Non-phthalate catalyst system and its use in the polymerization of olefins

ABSTRACT

This invention relates to a non-phthalate catalyst system for olefin polymerization. The non-phthalate catalyst system comprises (a) a solid Ziegler-Natta catalyst composition comprising a transition metal, a Group 2 metal, and one or more halogens; and one or more internal electron donor compounds; and (b) one or more external electron donor compounds.

This application is a continuation application of U.S. patentapplication Ser. No. 16/067,348, filed Jun. 29, 2018, which claimspriority to International PCT Patent Application No. PCT/US2016/069299,filed Dec. 29, 2016, which claims the benefit of priority to U.S.Provisional Patent Application Ser. No. 62/273,584, filed Dec. 31, 2015,and to U.S. Provisional Patent Application Ser. No. 62/278,256, filedJan. 13, 2016; all of which are hereby incorporated by reference intheir entirety.

FIELD OF THE INVENTION

This invention relates to a non-phthalate catalyst system with a novelexternal electron donor for olefin polymerization.

BACKGROUND OF THE INVENTION

Phthalate-based catalysts have been widely used in the commercialproduction of polypropylene worldwide. Extensive research anddevelopment have shown that the use of certain alkoxysilanes as externaldonors leads to optimum performance of phthalate-based catalysts(Kissin, Alkene Polymerizations with Transition Metal Catalysts, Studiesin Surface Science and Catalysis 173: 224-243 (Elsevier, Amsterdam,2007); Pasquini, Polypropylene Handbook (2^(nd) Ed., Hanser Publishers,Munich, 2005); Moore, The Rebirth of Polypropylene: Supported Catalysts(Hanser Publishers, Munich, 1998)). The use of these silane donorsallows for the production of a wide range of polypropylene products, dueto the varied effect of these donors on the hydrogen response(characterized by melt flow rate (MFR)), isotacticity (characterized by% xylene solubles (% XS) or the isotactic pentad contents (mmmm) of thexylene-insoluble fraction (XI)), and molecular weight distribution(MWD).

Yet the use of these phthalate-based catalysts has caused regulatory andhuman health and safety concerns. Non-phthalate catalysts have beenevaluated as replacements for the phthalate-based systems. However, thecurrent non-phthalate catalysts generally do not match the performanceof the phthalate systems.

Non-phthalate catalysts have certain limitations compared to thephthalate systems, for instance, very high initial activity, fast decayof polymerization activity, insufficient catalyst activity or low gasphase activity in sequential polymerization process for impact copolymerproduction. Additionally, non-phthalate catalysts often exhibit one ormore of the following characteristics: low hydrogen response(characterized by low MFR) and low isotacticity. These limitations ofthe non-phthalate catalysts often render the properties of the polymersmade with non-phthalate systems poorer than those of the polymers madewith the phthalate-based catalysts.

There thus remains a need in the art to improve the technology of thesenon-phthalate catalyst systems to overcome the above-describedlimitations in the non-phthalate catalyst systems. This inventionanswers that need.

SUMMARY OF THE INVENTION

One aspect of the invention relates to a non-phthalate catalyst systemfor olefin polymerization. The non-phthalate catalyst system comprises(a) a solid Ziegler-Natta catalyst composition comprising a transitionmetal, a Group 2 metal, and one or more halogens; and one or moreinternal electron donor compounds; and (b) one or more external electrondonor compounds.

The internal electron donor compound is i) a diether compound having aformula of

ii) a diester compound having a formula of

iii) a cyclic diester compound having a formula of

or iv) a succinate compound having a formula of

In these formulas, each of R₁ and R₂ is independently H or an alkyl,cycloalkyl, aryl, or aralkyl group, each having from 1 to 18 carbonatoms; or, R₁ and R₂ together form one or more saturated or unsaturatedmono- or poly-cyclic structures. Each R₃ is independently an alkyl,aryl, or aralkyl group having from 1 to 18 carbon atoms. Each R₄ is H orR₃. Each R₅ is independently a C₁ to C₁₈ hydrocarbyl group which canoptionally form one or more saturated or unsaturated mono- orpoly-cyclic structures. Each of R₆ and R₇ is independently H or a C₁ toC₁₈ hydrocarbyl group; or, R₆ and R₇ together form one or more saturatedor unsaturated mono- or poly-cyclic structures. Each R₈ is independentlyabsent, H, or a C₁ to C₁₈ hydrocarbyl group. Each R₉ is independently H,halogen, or a C₁ to C₁₈ hydrocarbyl group. Each R₁₀ is independently aC₁ to C₂₀ hydrocarbyl group. Each of R₁₁ and R₁₂ is independently R₉ or—COOR₁₀, provided that at least one of R₁₁ and R₁₂ is —COOR₁₀. Each ofR₁₃ and R₁₄ is independently a C₁ to C₁₈ hydrocarbyl group. The integerm is 0 or 1. The integer p ranges from 1 to 6. Each of R₁, R₂, R₃, R₄,R₅, R₆, R₇, R₈, R₉, R₁₃, and R₁₄ can contain one or more heteroatoms,selected from the group consisting of halogens, P, N, O, S, and Si, thatreplace one or more carbon atoms in the hydrocarbyl group.

The external electron donor compound is i) a triester compound having aformula of

ii) a diester compound having a formula of

or iii) an oxo-substituted diester compound having a formula of

In these formulas, X is CH₂ or O. Each R is independently a C₁-C₁₀hydrocarbyl group. Each R′ is independently H or R. Each n isindependently an integer from 1 to 4. The integer n′ ranges from 0 to 4.

Another aspect of the invention relates to a non-phthalate catalystsystem for olefin polymerization. The non-phthalate catalyst systemcomprises (a) a solid Ziegler-Natta catalyst composition comprising atransition metal, a Group 2 metal, and one or more halogens; and one ormore internal electron donor compounds; and (b) one or more externalelectron donor compounds.

The internal electron donor compound is i) a diester compound having aformula of

or ii) a cyclic diester compound having a formula of

In these formulas, each R₅ is independently a C₁ to C₁₈ hydrocarbylgroup which can optionally form one or more saturated or unsaturatedmono- or poly-cyclic structures. Each R₁₇ is independently H, halogen,or C₁ to C₁₈ hydrocarbyl group which can optionally form one or moresaturated or unsaturated cyclic structures with the phenyl group it isattached to. Each R₉ is independently H, halogen, or C₁ to C₁₈hydrocarbyl group. Each R₁₀ is independently C₁ to C₂₀ hydrocarbylgroup. Each of R₁₁ and R₁₂ is independently R₉ or —COOR₁₀, provided thatat least one of R₁₁ and R₁₂ is —COOR₁₀. Each m′ is independently aninteger from 0 to 5. The integer p ranges from 1 to 6. Each of R₅, R₉,and R₁₇ can contain one or more heteroatoms, selected from the groupconsisting of halogens, P, N, O, S, and Si, that replace one or morecarbon atoms in the hydrocarbyl group.

The external electron donor compound has a formula of

wherein the external electron donor compound does not contain analkoxysilane compound. In formula VIII, each R is independently a C₁ toC₁₀ hydrocarbyl group, and can contain one or more heteroatoms, selectedfrom the group consisting of halogens, P, N, O, S, and Si, that replaceone or more carbon atoms in the hydrocarbyl group. R′ is H or R. Theinteger n ranges from 1 to 10.

Another aspect of the invention relates to a process for preparing apolyolefin. The process comprises polymerizing one or more olefins, inthe presence of the non-phthalate catalyst system under reactionconditions sufficient to form the polyolefin. The non-phthalate catalystsystem may be any non-phthalate catalyst system described herein.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph showing the hydrogen responses of polymers preparedwith Example No. 2 procatalyst (non-phthalate) in combination with aconventional alkoxysilane external donor and non-silane aliphaticdiester external donors (1-gallon reactor, 75° C., ratio of donor/Ticompound=10), as compared to a phthalate procatalyst in combination witha conventional alkoxysilane external donor.

FIG. 2 is a graph showing the ethylene incorporation into an impactcopolymer using Example No. 3 procatalyst (non-phthalate) in combinationwith a conventional alkoxysilane external donor and non-silane esterexternal donors, as compared to a phthalate procatalyst (ComparativeExample 1) in combination with the conventional alkoxysilane externaldonor (2-gallon reactor, ratio of donor/Ti compound=10).

FIG. 3 is a graph showing the % XS in an impact copolymer using ExampleNo. 3 procatalyst (non-phthalate) in combination with a conventionalalkoxysilane external donor and non-silane ester external donors, ascompared to a phthalate procatalyst (Comparative Example 1) incombination with the conventional alkoxysilane external donor (2-gallonreactor, ratio of donor/Ti compound=10).

FIG. 4 is a graph showing the hydrogen responses of Example No. 1procatalyst (non-phthalate) in combination with conventionalalkoxysilane external donors and non-silane aliphatic diester externaldonors (1-gallon reactor, 75° C., ratio of donor/Ti compound=10).

DETAILED DESCRIPTION OF THE INVENTION

This invention relates to a non-phthalate catalyst system capable toproduce polyolefins with good catalyst activity, high isotacticity, andincreased hydrogen response. Previously, non-phthalate catalyst systemshave typically focused on using conventional alkoxysilane externaldonors. However, the non-phthalate catalysts often respond poorly to thechanges in the type of conventional alkoxysilane external donors used,and the conventional alkoxysilane external donors generally have littlemodifying effect on the performance of the non-phthalate catalysts andthe resulting polymer properties. In this invention, the inventors havediscovered a series of novel catalyst/non-silane external donor systemsthat are chemically different from catalyst/alkoxysilane external donorsystems. These non-silane external donors can modify the non-phthalatecatalysts more significantly than the well-known alkoxysilane externaldonors and, thus, significantly improving the performance of theresulting polymer.

One aspect of the invention relates to a non-phthalate catalyst systemfor olefin polymerization. The non-phthalate catalyst system comprises(a) a solid Ziegler-Natta catalyst composition comprising a transitionmetal, a Group 2 metal, and one or more halogens; and one or moreinternal electron donor compounds; and (b) one or more external electrondonor compounds.

The internal electron donor compound is i) a diether compound having aformula of

ii) a diester compound having a formula of

iii) a cyclic diester compound having a formula of

or iv) a succinate compound having a formula of

In these formulas, each of R₁ and R₂ is independently H or an alkyl,cycloalkyl, aryl, or aralkyl group, each having from 1 to 18 carbonatoms; or, R₁ and R₂ together form one or more saturated or unsaturatedmono- or poly-cyclic structures. Each R₃ is independently an alkyl,aryl, or aralkyl group having from 1 to 18 carbon atoms. Each R₄ is H orR₃. Each R₅ is independently a C₁ to C₁₈ hydrocarbyl group which canoptionally form one or more saturated or unsaturated mono- orpoly-cyclic structures. Each of R₆ and R₇ is independently H or a C₁ toC₁₈ hydrocarbyl group; or, R₆ and R₇ together form one or more saturatedor unsaturated mono- or poly-cyclic structures. Each R₈ is independentlyabsent, H, or a C₁ to C₁₈ hydrocarbyl group. Each R₉ is independently H,halogen, or a C₁ to C₁₈ hydrocarbyl group. Each R₁₀ is independently aC₁ to C₂₀ hydrocarbyl group. Each of R₁₁ and R₁₂ is independently R₉ or—COOR₁₀, provided that at least one of R₁₁ and R₁₂ is —COOR₁₀. Each ofR₁₃ and R₁₄ is independently a C₁ to C₁₈ hydrocarbyl group. The integerm is 0 or 1. The integer p ranges from 1 to 6. Each of R₁, R₂, R₃, R₄,R₅, R₆, R₇, R₈, R₉, R₁₃, and R₁₄ can contain one or more heteroatoms,selected from the group consisting of halogens, P, N, O, S, and Si, thatreplace one or more carbon atoms in the hydrocarbyl group.

The external electron donor compound is i) a triester compound having aformula of

ii) a diester compound having a formula of

or iii) an oxo-substituted diester compound having a formula of

In these formulas, X is CH₂ or O. Each R is independently a C₁-C₁₀hydrocarbyl group. Each R′ is independently H or R. Each n isindependently an integer from 1 to 4. The integer n′ ranges from 0 to 4.

Solid Ziegler-Nata Catalyst Composition

Catalyst systems for the stereospecific polymerization of olefins arewell known in the art. The most common type of catalyst system is theZiegler-Natta family, which comprises a solid catalyst compositioncontaining a Ziegler-Natta procatalyst composition, an internal electrondonor, and an external electron donor.

Any Ziegler-Natta procatalyst known in the art may be used in thenon-phthalate catalyst system. For instance, the Ziegler-Nattaprocatalyst composition typically contains a transition metal compoundand a Group 2 metal compound. The transition metal compound may be asolid complex derived from a transition metal compound, for example,titanium-, zirconium-, chromium- or vanadium-hydrocarbyloxides,hydrocarbyls, halides, or mixtures thereof. In a typical Ziegler-Nattaprocatalyst composition, the transition metal is titanium, the Group 2metal is magnesium, and the halogen is chloride.

The transition metal compound may have the general formulas of TrX_(x)or Tr(OQ)_(g)X_(4−g). Tr is the transition metal, for instance, Tr maybe a Group 4, 5, or 6 metal. In one embodiment, Tr is a Group 4 metal,such as titanium. In another embodiment, Tr is Group 5 metal, such asvanadium. Each Q independently represents a hydrocarbon group, such as aC₁-C₁₀ alkyl group. X represents a halogen atom, such as chloride,bromide, or iodide; x is an integer from 3 to 4; and g is an integerfrom 0 to 4. Exemplary transition metal compounds include titaniumtrihalides such as TiCl₃, TiBr₃, and TiI₃; titanium tetrahalides such asTiCl₄, TiBr₄, and TiI₄; alkoxytitanium trihalides such as Ti(OCH₃)Cl₃,Ti(OC₂H₅)Cl₃, Ti(OC₄H₉)Cl₃, Ti(OC₂H₅)Br₃, and Ti(OC₄H₉)Br₃;dialkoxytitanium dihalides such as Ti(OCH₃)₂Cl₂, Ti(OC₂H₅)₂Cl₂,Ti(OC₄H₉)₂Cl₂ and Ti(OC₂H₅)₂Br₂; trialkoxytitanium monohalides such asTi(OCH₃)₃Cl, Ti(OC₂H₅)₃Cl, Ti(OC₄H₉)₃Cl, and Ti(OC₂H₅)₃Br; andtetraalkoxytitaniums such as Ti(OCH₃)₄, Ti(OC₂H₅)₄ and Ti(OC₄H₉)₄.Mixtures of two or more such transition metal compounds may be used aswell. The transition metal compound may be used individually or insolutions of hydrocarbon compounds or halogenated hydrocarbons.

Suitable Group 2 metal compounds include magnesium halides, such asmagnesium chloride and magnesium bromide; alkoxymagnesiums, such asethoxymagnesium, isopropoxymagnesium, butoxymagnesium, and2-ethylhexoxymagnesium; dialkoxymagnesiums, such as diethoxymagnesium;alkoxymagnesium halides, such as methoxymagnesium chloride,ethoxymagnesium chloride, isopropoxy magnesium chloride, butoxymagnesium chloride, and octoxy magnesium chloride; magnesium oxyhalides;dialkylmagnesiums; aryloxymagnesiums, such as phenoxymagnesium andmethylphenoxy magnesium chloride; and carboxylates of magnesium, such asmagnesium laurate and magnesium stearate. These magnesium compounds maybe in the liquid or solid state. Typically, the Group 2 metal compoundis magnesium dichloride.

Internal Donor

The Ziegler-Natta procatalyst composition includes an internal electrondonor. The internal electron donor provides tacticity control andcatalyst crystallite sizing. Suitable internal electron donors includediethers, diesters, cyclic diesters, and succinates, and combinationsthereof.

As used herein, a “hydrocarbyl” is a linear or branched aliphaticradical, such as alkyl, alkenyl, and alkynyl; alicyclic radical, such ascycloalkyl, cycloalkenyl; aromatic radical, such as monocyclic orpolycyclic aromatic radical; as well as combinations thereof, such asalkaryl and aralkyl.

i) Diether Compound

The internal electron donor can be a diether compound, such as a1,3-diether having a formula of

Each of R₁ and R₂ is independently H or an alkyl, cycloalkyl, aryl, oraralkyl group, each having from 1 to 18 carbon atoms; or, R₁ and R₂together form one or more saturated or unsaturated mono- or poly-cyclicstructures. Each R₃ is independently an alkyl, aryl, or aralkyl grouphaving from 1 to 18 carbon atoms. Each R₄ is H or R₃. The alkyl,cycloalkyl, and aryl for each R group can be further substituted withone or more of alkyl, cycloalkyl, aryl, or halogen groups. Each of R₁,R₂, R₃, and R₄ can contain one or more heteroatoms, selected from thegroup consisting of halogens, P, N, O, S, and Si, that replace one ormore carbon atoms in the hydrocarbyl group. Typically, R₁ and R₂ areeach independently H, C₁-C₆ alkyl, C₂-C₁₀ mono- or di-cycloalkyl,phenyl, benzyl, or naphthyl; R₃ is a C₁-C₆ alkyl such as methyl; and R₄is hydrogen.

In some embodiments, when one of R₁ and R₂ is hydrogen, the other can beethyl, butyl, 2-ethylhexyl, cyclohexylethyl, diphenylmethyl,p-chlorophenyl, 1-naphthyl, or 1-decahydronaphthyl. In some embodiments,when one of R₁ and R₂ is methyl, ethyl, or propyl; the other can beethyl, propyl, butyl, pentyl, 2-ethylhexyl, cyclopentyl, cyclohexyl,methylcyclohexyl, phenyl, or benzyl. In some embodiments, both R₁ and R₂can be ethyl, propyl, isopropyl, butyl, pentyl, phenyl, benzyl,cyclohexyl, or cyclopentyl. Exemplary diether compounds include, but arenot limited to, 2-(2-ethylhexyl)-1,3-dimethoxypropane,2-isopropyl-1,3-dimethoxypropane, 2-butyl-1,3-dimethoxypropane,2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane,2-phenyl-1,3-dimethoxypropane, 2-tert-butyl-1,3-dimethoxypropane,2-cumyl-1,3-di4methoxypropane, 2-(2-phenylethyl)-1,3-dimethoxypropane,2-(2-cyclohexylethyl)-1,3-dimethoxypropane,2-(p-chlorophenyl)-1,3-dimethoxypropane,2-(diphenylmethyl)-1,3-dimethoxypropane, 2(1-naphthyl)-1,3-dimethoxypropane,2(p-fluorophenyl)-1,3-dimethoxypropane,2(1-decahydronaphthyl)-1,3-dimethoxypropane,2(p-tert-butylphenyl)-1,3-dimethoxypropane,2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane,2,2-dipropyl-1,3-dimethoxypropane, 2,2-dibutyl-1,3-dimethoxypropane,2,2-diethyl-1,3-diethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane,2,2-dipropyl-1,3-diethoxypropane, 2,2-dibutyl-1,3-diethoxypropane,2-methyl-2-ethyl-1,3-dimethoxypropane,2-methyl-2-propyl-1,3-dimethoxypropane,2-methyl-2-benzyl-1,3-dimethoxypropane,2-methyl-2-phenyl-1,3-dimethoxypropane,2-methyl-2-cyclohexyl-1,3-dimethoxypropane,2-methyl-2-methylcyclohexyl-1,3-dimethoxypropane,2,2-bis(p-chlorophenyl)-1,3-dimethoxypropane,2,2-bis(2-phenylethyl)-1,3-dimethoxypropane,2,2-bis(2-cyclohexylethyl)-1,3-dimethoxypropane,2-methyl-2-isobutyl-1,3-dimethoxypropane,2-methyl-2-(2-ethylhexyl)-1,3-dimethoxypropane,2,2-bis(2-ethylhexyl)-1,3-dimethoxypropane,2,2-bis(p-methylphenyl)-1,3-dimethoxypropane,2-methyl-2-isopropyl-1,3-dimethoxypropane,2,2-diisobutyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane,2,2-dibenzyl-1,3-dimethoxypropane,2-isopropyl-2-cyclopentyl-1,3-dimethoxypropane,2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane,2,2-diisobutyl-1,3-diethoxypropane, 2,2-diisobutyl-1,3-dibutoxypropane,2-isobutyl-2-isopropyl-1,3-dimethoxypropane,2,2-di-sec-butyl-1,3-dimetoxypropane,2,2-di-tert-butyl-1,3-dimethoxypropane,2,2-dineopentyl-1,3-dimethoxypropane,2-iso-propyl-2-isopentyl-1,3-dimethoxypropane,2-phenyl-2-benzyl-1,3-dimetoxypropane,2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane. Mixtures of two ormore such diether compounds may be used as well.

In some embodiments, R₁ and R₂ together form one or more unsaturatedmono- or poly-cyclic structures, such as cyclopentadiene. The resultingdiether compound has a formula of

R₃ and R₄ are defined as above. Each R₁′ is independently H, halogen, oran alkyl, cycloalkyl, aryl, or aralkyl group, each having from 1 to 18carbon atoms; or, two or more of R₁′, together with the pentadiene ring,form fused di- or tri-cyclic structures. The alkyl, cycloalkyl, and arylfor each R₁′ group can be further substituted with one or more of alkyl,cycloalkyl, aryl, or halogen groups. Each R₁′ and its substituent groupcan optionally contain one or more heteroatoms, selected from the groupconsisting of halogens, P, N, O, S, and Si, that replace one or morecarbon atoms. The integer r ranges from 0 to 4. Typically, R₃ is a C₁-C₆alkyl such as methyl; and R₄ is hydrogen. Typically, each R₁′ is H,halogen such as fluoro or chloro; C₁-C₆ alkyl; C₂-C₆ cycloalkyl; phenyl;or two of the R₁′ groups form an indene with the pentadiene ring.Exemplary pentadiene- or indiene-containing compounds are1,1-bis(methoxymethyl)-cyclopentadiene;1,1-bis(methoxymethyl)-2,3,4,5-tetramethylcyclopentadiene;1,1-bis(methoxymethyl)-2,3,4,5-tetraphenylcyclopentadiene;1,1-bis(methoxymethyl)-2,3,4,5-tetrafluorocyclopentadiene;1,1-bis(methoxymethyl)-3,4-dicyclopentylcyclopentadiene;1,1-bis(methoxymethyl)indene; 1,1-bis(methoxymethyl)-2,3-dimethylindene;1,1-bis(methoxymethyl)-4,5,6,7-tetrahydroindene;1,1-bis(methoxymethyl)-2,3,6,7-tetrafluoroindene;1,1-bis(methoxymethyl)-4,7-dimethylindene;1,1-bis(methoxymethyl)-3,6-dimethylindene;1,1-bis(methoxymethyl)-4-phenylindene;1,1-bis(methoxymethyl)-4-phenyl-2-methylindene;1,1-bis(methoxymethyl)-4-cyclohexylindene;1,1-bis(methoxymethyl)-7-(3,3,3-trifluoropropyl)indene;1,1-bis(methoxymethyl)-7-trimethyilsilylindene;1,1-bis(methoxymethyl)-7-trifluoromethylindene;1,1-bis(methoxymethyl)-4,7-dimethyl-4,5,6,7-tetrahydroindene;1,1-bis(methoxymethyl)-7-methylindene;1,1-bis(methoxymethyl)-7-cyclopentylindene;1,1-bis(methoxymethyl)-7-isopropylindene;1,1-bis(methoxymethyl)-7-cyclohexylindene;1,1-bis(methoxymethyl)-7-tert-butylindene;1,1-bis(methoxymethyl)-7-tert-butyl-2-methylindene;1,1-bis(methoxymethyl)-7-phenylindene;1,1-bis(methoxymethyl)-2-phenylindene;1,1-bis(methoxymethyl)-1H-benz[e]indene; and1,1-bis(methoxymethyl)-1H-2-methylbenz[e]indene. Mixtures of two or moresuch diether compounds may be used as well.

Alternatively, two or more of R₁′ groups, together with the pentadienering, form fused di- or tri-cyclic structures, such as fluorene. Theresulting diether compound has a formula of

R₃ and R₄ are defined as above. Each R₁₅ is independently H, halogen, oran alkyl, cycloalkyl, aryl, alkylaryl, or aralkyl group, each havingfrom 1 to 18 carbon atoms; or one or more R₁₅ groups, together with thebenzene ring, form fused rings. The integer q ranges from 0 to 4. Thesymbol “

” in the formula refers to a saturated bond or unsaturated bond.Typically, R₁₅ is H; halogen such as fluoro or chloro; C₁-C₆ alkyl;C₂-C₆ cycloalkyl; or two or more R₁₅ form benzofluorene with the benzenering(s). Exemplary fluorene-containing diether compounds are9,9-bis(methoxymethyl)fluorene;9,9-bis(methoxymethyl)-2,3,6,7-tetramethylfluorene;9,9-bis(methoxymethyl)-2,3,4,5,6,7-hexafluorofluorene;9,9-bis(methoxymethyl)-2,3-benzofluorene;9,9-bis(methoxymethyl)-2,3,6,7-dibenzofluorene;9,9-bis(methoxymethyl)-2,7-diisopropylfluorene;9,9-bis(methoxymethyl)-1,8-dichlorofluorene;9,9-bis(methoxymethyl)-2,7-dicyclopentylfluorene;9,9-bis(methoxymethyl)-1,8-difluorofluorene;9,9-bis(methoxymethyl)-1,2,3,4-tetrahydrofluorene;9,9-bis(methoxymethyl)-1,2,3,4,5,6,7,8-octahydrofluorene; and9,9-bis(methoxymethyl)-4-tert-butylfluorene. A typicalfluorene-containing diether compound is 9,9-bis(methoxymethyl)fluorene.Mixtures of two or more such diether compounds may be used as well.

ii) Diester Compound

The internal electron donor can be a diester compound having a formulaof

Each R₅ is independently a C₁ to C₁₈ hydrocarbyl group which canoptionally form one or more saturated or unsaturated mono- orpoly-cyclic structures. Each of R₆ and R₇ is independently H or a C₁ toC₁₈ hydrocarbyl group; or, R₆ and R₇ together form one or more saturatedor unsaturated mono- or poly-cyclic structures. Each R₈ is independentlyabsent, H, or a C₁ to C₁₈ hydrocarbyl group. The integer m is 0 or 1.Each of R₅, R₆, R₇, and R₈ can contain one or more heteroatoms, selectedfrom the group consisting of halogens, P, N, O, S, and Si, that replaceone or more carbon atoms in the hydrocarbyl group.

R₅ can be a C₁ to C₁₈ alkyl such as C₁ to C₁₀ alkyl; C₂ to C₁₈ alkenylsuch as C₂ to C₈ alkenyl; C₃ to C₁₈ cycloalkyl such as C₅ to C₆cycloalkyl; C₃ to C₁₈ cycloalkenyl such as C₅ to C₆ cycloalkenyl; arylsuch as phenyl; heteroaryl, e.g., 5- or 6-membered ring heteroaryl,containing one or more heteroatoms N, O, or S, such as furanyl; each ofthese groups can be further substituted by one or more halogen atomssuch as chloro or fluoro, C₁-C₁₀ alkyl, or C₁-C₁₀ alkyoxy. Each of R₆and R₇ can be independently C₁-C₁₅ alkyl (e.g., C₁-C₁₀ alkyl or C₁-C₆alkyl), C₆-C₁₄ aryl (e.g., phenyl), C₃-C₁₅ cycloalkyl (e.g., C₅-C₆cycloalkyl), C₇-C₁₅ arylalkyl (e.g., C₇-C₁₂ aralkyl), or C₇-C₁₅alkylaryl (e.g., C₇-C₁₂ alkylaryl). Each R₈ can be independently absent,hydrogen, C₁-C₁₅ alkyl (e.g., C₁-C₁₀ alkyl or C₁-C₆ alkyl), C₂ to C₁₈alkenyl (e.g., C₂ to C₈ alkenyl), C₆-C₁₄ aryl (e.g., phenyl, naphthyl,or halophenyl), C₃-C₁₅ cycloalkyl (e.g., C₅-C₆ cycloalkyl), C₇-C₁₅arylalkyl (e.g., C₇-C₁₂ aralkyl), or C₇-C₁₅ alkylaryl (e.g., C₇-C₁₂alkylaryl).

In some embodiments, m is 1. The diester compound has a formula of:

R₅, R₆, R₇, and R₈ are defined as above. In certain embodiments, each R₅is independently an aryl. For instance, the diester compound can have aformula of:

Each R₁₆ is independently H, halogen, or a C₁ to C₁₈ hydrocarbyl groupwhich can optionally form one or more saturated or unsaturated cyclicstructures with the phenyl group it attaches to. Each R₁₆ can containone or more heteroatoms, selected from the group consisting of halogens,P, N, O, S, and Si, that replace one or more carbon atoms in thehydrocarbyl group. For instance, each R₁₆ can be independently H,halogen, a C₁-C₁₅ alkyl (e.g., C₁-C₁₀ alkyl or C₁-C₆ alkyl), C₁-C₁₅alkoxy (e.g., C₁-C₁₀ alkoxy or C₁-C₆ alkoxy), C₆-C₁₄ aryl (e.g.,phenyl), C₃-C₁₅ cycloalkyl, C₇-C₁₅ arylalkyl (e.g., C₇-C₁₂ aralkyl), orC₇-C₁₅ alkylaryl (e.g., C₇-C₁₂ alkylaryl). Exemplary R₁₆ groups are H,halogen such as chloro or fluoro, a C₁-C₆ alkyl, C₁-C₆ alkoxy, phenyl,C₇-C₁₂ aralkyl, or C₇-C₁₂ alkylaryl. Each m′ is independently an integerfrom 0 to 5, for instance, from 0 to 3. Exemplary R₆ and R₇ groups areC₁-C₆ alkyl, phenyl, C₅-C₆ cycloalkyl, C₇-C₁₂ arylalkyl, or C₇-C₁₂alkylaryl. Exemplary R₈ groups are hydrogen; C₁-C₆ alkyl; C₂ to C₈alkenyl; phenyl, naphthyl, or halophenyl; C₅-C₆ cycloalkyl; C₇-C₁₂arylalkyl; or C₇-C₁₂ alkylaryl.

Exemplary diester compounds for formula IIb are 2,4-pentanedioldibenzoate, 3-methyl-2,4-pentanediol dibenzoate, 3-ethyl-2,4-pentanedioldibenzoate, 3-n-propyl-2,4-pentanediol dibenzoate,3-i-propyl-2,4-pentanediol dibenzoate, 3-n-butyl-2,4-pentanedioldibenzoate, 3-i-butyl-2,4-pentanediol dibenzoate,3-t-butyl-2,4-pentanediol dibenzoate, 3-n-pentyl-2,4-pentanedioldibenzoate, 3-i-pentyl-2,4-pentanediol dibenzoate,3-cyclopentyl-2,4-pentanediol dibenzoate, 3-cyclohexyl-2,4-pentanedioldibenzoate, 3-phenyl-2,4-pentanediol dibenzoate,3-(2-naphtyl)-2,4-pentanediol dibenzoate, 3-allyl-2,4-pentanedioldibenzoate, 3,3-dimethyl-2,4-pentanediol dibenzoate,3-ethyl-3-methyl-2,4-pentanediol dibenzoate,3-methyl-3-i-propyl-2,4-pentanediol dibenzoate,3,3-diisopropyl-2,4-pentanediol dibenzoate,3-i-pentyl-2-i-propyl-2,4-pentanediol dibenzoate, 3,5-heptanedioldibenzoate, 4,6-nonanediol dibenzoate, 2,6-dimethyl-3,5-heptanedioldibenzoate, 5,7-undecanediol dibenzoate, 2,8-dimethyl-4,6-nonanedioldibenzoate, 2,2,6,6,tetramethyl-3,5-hetanediol dibenzoate,6,8-tridecanediol dibenzoate, 2,10-dimethyl-5,7-undecanediol dibenzoate,1,3-dicyclopentyl-1,3-propanediol dibenzoate,1,3-dicyclohexyl-1,3-propanediol dibenzoate,1,3-diphenyl-1,3-propanediol dibenzoate,1,3-bis(2-naphtyl)-1,3-propanediol dibenzoate, 2,4-hexanedioldibenzoate, 2,4-heptanediol dibenzoate, 2-methyl-3,5-hexanedioldibenzoate, 2,4-octanediol dibenzoate, 2-methyl-4,6-heptanedioldibenzoate, 2,2-dimethyl-3,5-hexanediol dibenzoate,2-methyl-5,7-octanediol dibenzoate, 2,4-nonanediol dibenzoate,1-cyclopentyl-1,3-butanediol dibenzoate, 1-cyclohexyl-1,3-butanedioldibenzoate, 1-phenyl-1,3-butanediol dibenzoate,1-(2-naphtyl)-1,3-butanediol dibenzoate,2,4-pentanediol-bis(4-methylbenzoate),2,4-pentanediol-bis(3-methylbenzoate),2,4-pentanediol-bis(4-ethylbenzoate),2,4-pentanediol-bis(4-n-propylbenzoate),2,4-pentanediol-bis(4-n-butylbenzoate),2,4-pentanediol-bis(4-i-propylbenzoate),2,4-pentanediol-bis(4-i-butylbenzoate),2,4-pentanediol-bis(4-t-butylbenzoate),2,4-pentanediol-bis(4-phenylbenzoate),2,4-pentanediol-bis(3,4-dimethylbenzoate),2,4-pentanediol-bis(2,4,6-trimethylbenzoate),2,4-pentanediol-bis(2,6-dimethylbenzoate),2,4-pentanediol-di-(2-naphthoate),3-methyl-2,4-pentanediol-bis(4-n-propylbenzoate),3-i-pentyl-2,4-pentanediol-bis(4-n-propylbenzoate),1,1,1,5,5,5-hexafluoro-2,4-pentanediol-bis(4-ethylbenzoate),1,1,1-trifluoro-2,4-pentanediol-bis(4-ethylbenzoate),1,3-bis(4-chlorophenyl)-1,3-propanediol-bis(4-ethylbenzoate),1-(2,3,4,5,6-pentafluorophenyl)-1,3-butanediol-bis(4-ethylbenzoate),1,1-difluoro-4-phenyl-2,4-butandiol-bis(4-n-propylbenzoate),1,1,1-trifluoro-5,5-dimethyl-2,4-hexandiol-bis(4-n-propylbenzoate),1,1,1-trifluoro-4-(2-furyl)-2,4-butandiol-bis(4-n-propylbenzoate),1,1,1-trifluoro-4-phenyl-2,4-butandiol-bis(4-n-propylbenzoate),1,1,1-trifluoro-4-(2-thienyl)-2,4-butandiol-bis(4-n-propylbenzoate),1,1,1-trifluoro-4-(4-chloro-phenyl)-2,4-butandiol-bis(4-n-propylbenzoate),1,1,1-trifluoro-4-(2-naphtyl)-2,4-butandiol-bis(4-n-propylbenzoate), and3-chloro-2,4-pentandiol-bis(4-n-propylbenzoate).

In some embodiments, m is 0, and R₆ and R₇ can form one or moresaturated or unsaturated mono- or poly-cyclic structures. For instance,R₆ and R₇ can form an aryl group having the formula of:

R₅ is defined as above. In certain embodiments, both R₅ groups are anaryl. For instance, the diester compound can have a formula of:

Each of R₁₆ and R₁₇ is independently H, halogen, or a C₁ to C₁₈hydrocarbyl group which can optionally form one or more saturated orunsaturated cyclic structures with the phenyl group it attaches to. Eachof R₁₆ and R₁₇ can contain one or more heteroatoms, selected from thegroup consisting of halogens, P, N, O, S, and Si, that replace one ormore carbon atoms in the hydrocarbyl group. For instance, each of R₁₆and R₁₇ can be independently H, halogen (e.g., chloro or fluoro), or aC₁-C₁₅ alkyl (e.g., C₁-C₁₀ alkyl or C₁-C₆ alkyl), C₁-C₁₅ alkoxy (e.g.,C₁-C₁₀ alkoxy or C₁-C₆ alkoxy), C₆-C₁₄ aryl (e.g., phenyl), C₃-C₁₅cycloalkyl, C₇-C₁₅ arylalkyl (e.g., C₇-C₁₂ aralkyl), or C₇-C₁₅ alkylaryl(e.g., C₇-C₁₂ alkylaryl). Exemplary R₁₆ and R₁₇ groups are H, halogensuch as chloro or fluoro, a C₁-C₆ alkyl, C₁-C₆ alkoxy, phenyl, C₇-C₁₂aralkyl, or C₇-C₁₂ alkylaryl. Each m′ is independently an integer from 0to 5, for instance, from 0 to 3. Exemplary compounds for formula IIdinclude those containing one or two R₁₇ groups and one R₁₆ on eachbenzoate moiety. For instance, exemplary compounds for formula IId cancontain two R₁₇ groups, one at para-position and one at ortho-positionto the —O—C(O)— group; and can contain one R₁₆ on each benzoate moiety,each at para-position to the —C(O)—O— group. A typical compound forformula IId is 5-(tert-butyl)-3-methyl-1,2-phenylene dibenzoate.

In some embodiments, m is 1, R₈ is absent, and R₆ and R₇ can form afused ring structure. For instance, R₆ and R₇ can form a naphthalenegroup, forming a 1,8-naphthalene diester compound having the formula of:

R₅ is defined as above. Each R₁₇ is independently H, halogen, or a C₁ toC₁₈ hydrocarbyl group which can optionally form one or more saturated orunsaturated cyclic structures with the phenyl group it attaches to. EachR₁₇ can contain one or more heteroatoms, selected from the groupconsisting of halogens, P, N, O, S, and Si, that replace one or morecarbon atoms in the hydrocarbyl group. For instance, each R₁₇ can beindependently H, halogen (e.g., chloro or fluoro), or a C₁-C₁₅ alkyl(e.g., C₁-C₁₀ alkyl or C₁-C₆ alkyl), C₁-C₁₅ alkoxy (e.g., C₁-C₁₀ alkoxyor C₁-C₆ alkoxy), C₆-C₁₄ aryl (e.g., phenyl), C₃-C₁₅ cycloalkyl, C₇-C₁₅arylalkyl (e.g., C₇-C₁₂ aralkyl), or C₇-C₁₅ alkylaryl (e.g., C₇-C₁₂alkylaryl). Exemplary R₁₇ groups are H, halogen such as chloro orfluoro, a C₁-C₆ alkyl, C₁-C₆ alkoxy, phenyl, C₇-C₁₂ aralkyl, or C₇-C₁₂alkylaryl. Each m′ is independently an integer from 0 to 5, forinstance, from 0 to 3.

In formula IIe, exemplary R₅ groups are C₁-C₁₀ alkyl; C₂-C₁₀ alkenyl;C₅-C₆ cycloalkyl; C₅-C₆ cycloalkenyl; aryl such as phenyl; orheteroaryl, e.g., 5- or 6-membered ring heteroaryl, containing one ormore heteroatoms N, O, or S, such as furanyl; each of these groups canbe further substituted by one or more halogen atoms such as chloro orfluoro, C₁-C₁₀ alkyl, or C₁-C₁₀ alkyoxy. R₅ may be the same ordifferent.

In certain embodiments, both R₅ groups are an aryl. For instance, the1,8-napthalene diester compound can have a formula of:

The definition of R₁₆ is the same as the definition of R₁₇, which isdefined above. The integer m′ is defined as above. Exemplary1,8-napthalene diester compounds for formula IIf are 1,8-naphthyldibenzoate; 1,8-naphthyl di-4-methylbenzoate; 1,8-naphthyldi-3-methylbenzoate; 1,8-naphthyl di-2-methylbenzoate; 1,8-naphthyldi-4-ethylbenzoate; 1,8-naphthyl di-4-n-propylbenzoate; 1,8-naphthyldi-4-isopropylbenzoate; 1,8-naphthyl di-4-n-butylbenzoate; 1,8-naphthyldi-4-isobutylbenzoate; 1,8-naphthyl di-4-t-butylbenzoate; 1,8-naphthyldi-4-phenylbenzoate; 1,8-naphthyl di-4-fluorobenzoate; 1,8-naphthyldi-3-fluorobenzoate; 1,8-naphthyl di-2-fluorobenzoate; 1,8-naphthyldi-4-chlorobenzoate; 1,8-naphthyl di-3-chlorobenzoate; 1,8-naphthyldi-2-chlorobenzoate; 1,8-naphthyl di-4-bromobenzoate; 1,8-naphthyldi-3-bromobenzoate; 1,8-naphthyl di-2-bromobenzoate; 1,8-naphthyldi-4-cyclohexylbenzoate; 1,8-naphthyl di-2,3-dimethylbenzoate;1,8-naphthyl di-2,4-dimethylbenzoate; 1,8-naphthyldi-2,5-dimethylbenzoate; 1,8-naphthyl di-2,6-dimethylbenzoate;1,8-naphthyl di-3,4-dimethylbenzoate; 1,8-naphthyldi-3,5-dimethylbenzoate; 1,8-naphthyl di-2,3-dichlorobenzoate;1,8-naphthyl di-2,4-dichlorobenzoate; 1,8-naphthyldi-2,5-dichlorobenzoate; 1,8-naphthyl di-2,6-dichlorobenzoate;1,8-naphthyl di-3,4-dichlorobenzoate; 1,8-naphthyldi-3,5-dichlorobenzoate; and 1,8-naphthyl di-3,5-di-t-butylbenzoate. Atypical diester compound for formula IIf is 1,8-naphthyl dibenzoate.

Additional exemplary 1,8-napthalene diester compounds for formula IIeare

iii) Cyclic Diester Compound

The internal electron donor can be a cyclic diester compound having aformula of

Each R₉ is independently H, halogen, or a C₁ to C₁₈ hydrocarbyl group.R₉ can contain one or more heteroatoms, selected from the groupconsisting of halogens, P, N, O, S, and Si, that replace one or morecarbon atoms in the hydrocarbyl group. For instance, R₉ can be C₁ to C₁₈alkyl such as C₁ to C₈ alkyl; C₂ to C₁₈ alkenyl such as C₂ to C₈alkenyl; C₃ to C₁₈ cycloalkyl such as C₅ to C₆ cycloalkyl; aryl such asphenyl; C₁ to C₁₈ alkoxy such as C₁ to C₈ alkoxy; siloxy; aldehyde; oracetyl. Exemplary R₉ groups are methyl, ethyl, n-propyl, isopropyl,n-butyl, isobutyl, sec-butyl, n-pentyl, cyclopentyl, n-hexyl,cyclohexyl, octyl, vinyl, or phenyl. Typically, R₉ is methyl, ethyl,n-propyl, isopropyl, n-butyl, isobutyl, or sec-butyl. Two or more R₉groups may also be bonded to each other to form a saturated orunsaturated mono- or poly-cyclic structure backbone, e.g., a fused ringand/or bridged polycyclic backbone. Exemplary fused ring and/or bridgedpolycyclic backbone are norbornane

and tetracyclododecene

Each R₁₀ is independently a C₁ to C₂₀ hydrocarbyl group. For example,R₁₀ can be a C₁ to C₂₀ alkyl, C₁ to C₁₀ alkyl, C₂ to C₈ alkyl, or C₄ toC₈ alkyl. Exemplary R₁₀ groups are ethyl, n-propyl, isopropyl, n-butyl,isobutyl, hexyl, heptyl, octyl, 2-ethylhexyl, decyl, dodecyl,tetradecyl, hexadecyl, octadecyl, or eicosyl. Typically, R₁₀ is n-butylor isobutyl.

Each R₁₁ and R₁₂ is independently R₉ or —COOR₁₀, provided that at leastone of R₁₁ and R₁₂ is —COOR₁₀.

The integer p ranges from 1 to 6. For instance p can be 1, 2, 3.Typically, p is 2.

In some embodiments, the cyclic diester compound has a formula of

In formulas IIIa and IIIb, each R₁₀ is independently a C₁ to C₁₀ alkyl,and each R₉ is independently H or a C₁ to C₈ alkyl, C₃ to C₆ cycloalkyl,C₂ to C₆ alkenyl, or phenyl. Exemplary cyclic diester compounds forformulas IIIa and IIIb are diisobutyl cyclohexane-1,2-dicarboxylate,diethyl 3-methylcyclohexane-1,2-dicarboxylate, di-n-propyl3-methylcyclohexane-1,2-dicarboxylate, diisopropyl3-methylcyclohexane-1,2-dicarboxylate, di-n-butyl 3-methylcyclohexane-1,2-dicarboxylate, diisobutyl3-methylcyclohexane-1,2-dicarboxylate, dihexyl3-methylcyclohexane-1,2-dicarboxylate, diheptyl3-methylcyclohexane-1,2-dicarboxylate, dioctyl3-methylcyclohexane-1,2-dicarboxylate, di-2-ethylhexyl3-methylcyclohexane-1,2-dicarboxylate, didecyl 3-methylcyclohexane-1,2-dicarboxylate, diethyl4-methylcyclohexane-1,3-dicarboxylate, diisobutyl4-methylcyclohexane-1,3-dicarboxylate, diethyl4-methylcyclohexane-1,2-dicarboxylate, di-n-propyl4-methylcyclohexane-1,2-dicarboxylate, diisopropyl4-methylcyclohexane-1,2-dicarboxylate, di-n-butyl4-methylcyclohexane-1,2-dicarboxylate, diisobutyl4-methylcyclohexane-1,2-dicarboxylate, dihexyl4-methylcyclohexane-1,2-dicarboxylate, diheptyl4-methylcyclohexane-1,2-dicarboxylate, dioctyl4-methylcyclohexane-1,2-dicarboxylate, di-2-ethylhexyl4-methylcyclohexane-1,2-dicarboxylate, didecyl4-methylcyclohexane-1,2-dicarboxylate, diethyl5-methylcyclohexane-1,3-dicarboxylate, diisobutyl5-methylcyclohexane-1,3-dicarboxylate, diethyl3,4-dimethylcyclohexane-1,2-dicarboxylate, di-n-propyl3,4-dimethylcyclohexane-1,2-dicarboxylate, diisopropyl3,4-dimethylcyclohexane-1,2-dicarboxylate, di-n-butyl3,4-dimethylcyclohexane-1,2-dicarboxylate, diisobutyl3,4-dimethylcyclohexane-1,2-dicarboxylate, dihexyl3,4-dimethylcyclohexane-1,2-dicarboxylate, diheptyl3,4-dimethylcyclohexane-1,2-dicarboxylate, dioctyl3,4-dimethylcyclohexane-1,2-dicarboxylate, di-2-ethylhexyl3,4-dimethylcyclohexane-1,2-dicarboxylate, didecyl3,4-dimethylcyclohexane-1,2-dicarboxylate, diethyl3,6-dimethylcyclohexane-1,2-dicarboxylate, di-n-propyl3,6-dimethylcyclohexane-1,2-dicarboxylate, diisopropyl3,6-dimethylcyclohexane-1,2-dicarboxylate, di-n-butyl3,6-dimethylcyclohexane-1,2-dicarboxylate, diisobutyl3,6-dimethylcyclohexane-1,2-dicarboxylate, dihexyl3,6-dimethylcyclohexane-1,2-dicarboxylate, diheptyl3,6-dimethylcyclohexane-1,2-dicarboxylate, dioctyl3,6-dimethylcyclohexane-1,2-dicarboxylate, di-2-ethylhexyl3,6-dimethylcyclohexane-1,2-dicarboxylate, didecyl3,6-dimethylcyclohexane-1,2-dicarboxylate, diethyl3,6-diphenylcyclohexane-1,2-dicarboxylate, di-n-propyl3,6-diphenylcyclohexane-1,2-dicarboxylate, diisopropyl3,6-diphenylcyclohexane-1,2-dicarboxylate, di-n-butyl3,6-diphenylcyclohexane-1,2-dicarboxylate, diisobutyl3,6-diphenylcyclohexane-1,2-dicarboxylate, dihexyl3,6-diphenylcyclohexane-1,2-dicarboxylate, dioctyl3,6-diphenylcyclohexane-1,2-dicarboxylate, didecyl3,6-diphenylcyclohexane-1,2-dicarboxylate, diethyl3-methyl-6-ethylcyclohexane-1,2-dicarboxylate, di-n-propyl3-methyl-6-ethylcyclohexane-1,2-dicarboxylate, diisopropyl3-methyl-6-ethylcyclohexane-1,2-dicarboxylate, di-n-butyl3-methyl-6-ethylcyclohexane-1,2-dicarboxylate, diisobutyl3-methyl-6-ethylcyclohexane-1,2-dicarboxylate, dihexyl3-methyl-6-ethylcyclohexane-1,2-dicarboxylate, diheptyl3-methyl-6-ethylcyclohexane-1,2-dicarboxylate, dioctyl3-methyl-6-ethylcyclohexane-1,2-dicarboxylate, di-2-ethylhexyl3-methyl-6-ethylcyclohexane-1,2-dicarboxylate, didecyl3-methyl-6-ethylcyclohexane-1,2-dicarboxylate, diethyl3-methyl-6-ethylcyclohexane-1,2-dicarboxylate, di-n-propyl3-methyl-6-ethylcyclohexane-1,2-dicarboxylate, diisopropyl3-methyl-6-ethylcyclohexane-1,2-dicarboxylate, di-n-butyl3-methyl-6-ethylcyclohexane-1,2-dicarboxylate, diisobutyl3-methyl-6-ethylcyclohexane-1,2-dicarboxylate, dihexyl3-methyl-6-ethylcyclohexane-1,2-dicarboxylate, diheptyl3-methyl-6-ethylcyclohexane-1,2-dicarboxylate, dioctyl3-methyl-6-ethylcyclohexane-1,2-dicarboxylate, di-2-ethylhexyl3-methyl-6-ethylcyclohexane-1,2-dicarboxylate, didecyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate, diethyl3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate, di-n-propyl3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate, diisopropyl3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate, di-n-butyl3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate, diisobutyl3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate, dihexyl3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate, diheptyl3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate, dioctyl3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate, di-2-ethylhexyl3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate, dodecyl3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate, diethyl3-hexylcyclohexane-1,2-dicarboxylate, diisobutyl3-hexylcyclohexane-1,2-dicarboxylate, diethyl3,6-dihexylcyclohexane-1,2-dicarboxylate, and diisobutyl3-hexyl-6-pentylcyclohexane-1,2-dicarboxylate. Typically, the cyclicdiester compound is diisobutyl cyclohexane-1,2-dicarboxylate ordiisobutyl 3,6-dimethylcyclohexane-1,2-dicarboxylate. Mixtures of two ormore such cyclic diester compounds may be used as well.

iv) Succinate Compound

The internal electron donor can be a succinate compound having a formulaof

Each of R₁₃ and R₁₄ is independently a C₁ to C₁₈ hydrocarbyl group. Forinstance, each of R₁₃ and R₁₄ can be C₁ to C₁₈ alkyl, C₂ to C₁₈ alkenyl,C₃ to C₁₈ cycloalkyl, or aryl. The alkyl, alkenyl, cycloalkyl, and arylfor each R group can be further substituted with one or more of alkyl,cycloalkyl, aryl, or halogen groups. Each of R₁₃ and R₁₄ can contain oneor more heteroatoms, selected from the group consisting of halogens, P,N, O, S, and Si, that replace one or more carbon atoms in thehydrocarbyl group. Typically, R₁₃ is C₁ to C₆ alkyl, C₅-C₆ cycloalkyl,phenyl, fluorenyl; each of these groups can be optionally substitutedwith one or more of C₁ to C₆ alkyl, C₅-C₆ cycloalkyl, phenyl, or halogenatoms such as fluoro or chloro. Typically, R₁₄ is C₁ to C₆ alkyl.

Exemplary succinate compounds are diethyl 2-sec-butyl-3-methylsuccinate,diethyl 2-(3,3,3-trifluoropropyl)-3-methylsuccinate, diethyl2,3-bis(2-ethylbutyl) succinate, diethyl2,3-diethyl-2-isopropylsuccinate, diethyl2,3-diisopropyl-2-methylsuccinate, diethyl2,3-dicyclohexyl-2-methylsuccinate, diethyl 2,3-dibenzylsuccinate,diethyl 2,3-diisopropylsuccinate, diethyl2,3-bis(cyclohexylmethyl)succinate, diethyl 2,3-di-t-butylsuccinate,diethyl 2,3-diisobutylsuccinate, diethyl 2,3-dineopentylsuccinate,diethyl 2,3-diisopentylsuccinate, diethyl2,3-(1-trifluoromethyl-ethyl)succinate, diethyl2-(9-fluorenyl)succinate, diethyl 2-isopropyl-3-isobutylsuccinate,diethyl 2-t-butyl-3-isopropylsuccinate, diethyl2-isopropyl-1,3-cyclohexylsuccinates diethyl2-isopentyl-3-cyclohexylsuccinate, diethyl2-cyclohexyl-3-cyclopentylsuccinate, diethyl2,2,3,3-tetramethylsuccinate, diethyl 2,2,3,3-tetraethylsuccinate,diethyl 2,2,3,3-tetra-n-propylsuccinate, diethyl2,3-diethyl-2,3-diisopropylsuccinate, diisobutyl2,3-bis(trimethylsilyl)succinate, diisobutyl2-sec-butyl-3-methylsuccinate, diisobutyl2-(3,3,3-trifluoropropyl)-3-methylsuccinate, diisobutyl2,3-bis(2-ethylbutyl)succinate, diisobutyl2,3-diethyl-2-isopropylsuccinate, diisobutyl2,3-diisopropyl-2-methylsuccinate, diisobutyl2,3-dicyclohexyl-2-methylsuccinate, diisobutyl 2,3-dibenzylsuccinate,diisobutyl 2,3-diisopropylsuccinate, diisobutyl2,3-bis(cyclohexylmethyl)succinate, diisobutyl 2,3-di-t-butylsuccinate,diisobutyl 2,3-diisobutyl succinate, diisobutyl2,3-dineopentylsuccinate, diisobutyl 2,3-diisopentylsuccinate,diisobutyl 2,3-bis(3,3,3-trifluoropropyl)succinate, diisobutyl2,3-di-n-propylsuccinate, diisobutyl 2-(9-fluorenyl)succinate,diisobutyl 2-isopropyl-3-isobutylsuccinate, diisobutyl2-t-butyl-3-isopropylsuccinate, diisobutyl2-isopropyl-3-cyclohexylsuccinate, diisobutyl2-isopentyl-3-cyclohexylsuccinate, diisobutyl2-n-propyl-3-(cyclohexylmethyl)succinate, diisobutyl2-cyclohexyl-3-cyclopentylsuccinate, diisobutyl2,2,3,3-tetramethylsuccinate, diisobutyl 2,2,3,3-tetraethyl succinate,diisobutyl 2,2,3,3-tetra-n-propylsuccinate, diisobutyl2,3-diethyl-2,3-diisopropylsuccinate, dineopentyl2,3-bis(trimethylsilyl)succinate, dineopentyl2,2-di-sec-butyl-3-methylsuccinate, dineopentyl2-(3,3,3-trifluoropropyl)-3-methylsuccinate, dineopentyl 2,3bis-(2-ethylbutyl)succinate, dineopentyl2,3-diethyl-2-isopropylsuccinate, dineopentyl2,3-diisopropyl-2-methylsuccinate, dineopentyl2,3-dicyclohexyl-2-methylsuccinate, dineopentyl 2,3-dibenzylsuccinate,dineopentyl 2,3-diisopropylsuccinate, dineopentyl2,3-bis-(cyclohexylmethyl)succinate, dineopentyl2,3-di-t-butylsuccinate, dineopentyl 2,3-diisobutyl succinate,dineopentyl 2,3-dineopentyl succinate, dineopentyl2,3-diisopentylsuccinate, dineopentyl2,3-bis(3,3,3-trifluoropropyl)succinate, dineopentyl2,3-n-propylsuccinate, dineopentyl 2-(9-fluorenyl)succinate, dineopentyl2-isopropyl-3-isobutylsuccinate, dineopentyl2-t-butyl-3-isopropylsuccinate, dineopentyl2-isopropyl-3-cyclohexylsuccinate, dineopentyl2-isopentyl-3-cyclohexylsuccinate, dineopentyl2-n-propyl-3-(cyclohexylmethyl)succinate, dineopentyl2-cyclohexyl-3-cyclopentylsuccinate, dineopentyl2,2,3,3-tetramethylsuccinate, dineopentyl 2,2,3,3-tetra-ethylsuccinate,dineopentyl 2,2,3,3-tetra-n-propylsuccinate, dineopentyl2,3-diethyl-2,3-diisopropylsuccinate, diethyl1,2-cyclohexanedicarboxylate, and diethyl norbornene-2,3-dicarboxylate.Typically, the succinate compound is diethyl 2,3-diisopropylsuccinate.Mixtures of two or more such succinate compounds may be used as well.

Preparation of Solid Ziegler-Nata Catalyst Composition

The solid Ziegler-Nata procatalyst composition can be carried out byvarious methods known to one skilled in the art. For instance, thetitanium compound, the magnesium dichloride in an anhydrous state, andthe electron donor compounds can be milled together under conditions inwhich activation of the magnesium dichloride occurs. The product can betreated one or more times with an excess of TiCl₄ at a temperature about80 to 135° C., followed by washings with hydrocarbon solvents untilchloride ions disappear. Alternatively, magnesium dichloride ispreactivated by methods known to one skilled in the art, and thentreated with an excess of TiCl₄ at a temperature of about 80 to 135° C.in the presence of the electron donor compounds. The treatment withTiCl₄ can be repeated and the solid can be washed with a hydrocarbonsolvent such as hexane to eliminate any non-reacted TiCl₄.

In another example, the titanium compound, the magnesium chloride in ananhydrous state, the electron donor compounds can be milled togetherunder conditions in which activation of the magnesium chloride occurs.The product can be treated with halogenated hydrocarbons such as1,2-dichloroethane, chlorobenzene, dichloromethane, etc., for about 1and 4 hours and at temperature of from 40° C. to the boiling point ofthe halogenated hydrocarbon. The product is then washed with inerthydrocarbon solvents such as hexane.

In another example, the solid catalyst component can be prepared byreacting a titanium compound of formula TiX_(x) or Ti(OQ)_(g)X_(4−g)with a magnesium chloride deriving from an adduct of formula(MgCl₂)_(p)ROH, in which p is a number between 0.1 and 6, for instance,between 2 to 3.5; and R is a C₁-C₁₈ hydrocarbyl. The adduct can besuitably prepared in spherical form by mixing alcohol and magnesiumchloride in the presence of an inert hydrocarbon immiscible with theadduct, operating under stirring conditions at the melting temperatureof the adduct (100-130° C.). The emulsion can then be quenched, causingthe solidification of the adduct in form of spherical particles.Examples of spherical adducts prepared according to this procedure aredescribed in U.S. Pat. Nos. 4,399,054 and 4,469,648, which areincorporated herein by reference in their entirety. The obtained adductcan be directly reacted with the titanium compound. Alternatively, theobtained adduct can be first subjected to thermally controlleddealcoholation (at 80-130° C.) to obtain an adduct in which the numberof moles of alcohol is generally lower than 3, for instance, between 0.1and 2.5. The reaction of the adduct with the titanium compound can becarried out by suspending the adduct (dealcoholated or not) in coldTiCl₄ (generally at 0° C.), and heating the mixture to about 80-130° C.(the temperature can be kept at this range for about 0.5-2 hours). Thetreatment with TiCl₄ can be carried out one or more times. The electrondonor compounds can be added during the treatment with TiCl₄, and can beadded together in the same treatment with TiCl₄ or separately in two ormore treatments.

The preparations of the solid catalyst components in spherical forms aredescribed, for example, in WO98/44001 and U.S. Patent ApplicationPublication No. 2013/0197173, which are incorporated herein by referencein their entirety.

The solid Ziegler-Nata procatalyst composition can contain from about0.5 to about 6.0 wt % titanium; from about 10 to about 25 wt %magnesium; from about 40 to about 70 wt % halogen; from about 1 to about50 wt % internal electron donor compound; and optionally inert diluentfrom about 0 to about 15 wt %. For instance, the Ziegler-Nataprocatalyst composition contains from about 2 to about 20 wt % of one ormore of the internal electron donor compounds, or from about 5 to about15 wt % of one or more of the internal electron donor compounds.

The amounts of the components used in preparing the solid Ziegler-Nataprocatalyst composition may vary depending upon the method ofpreparation. For instance, from about 0.01 to about 5 moles of the totalinternal electron donor compounds and from about 0.01 to about 500 molesof the titanium compound are used per mole of the magnesium compoundused to make the solid procatalyst composition. Typically, from about0.05 to about 2 moles of the total internal electron donor compounds andfrom about 0.05 to about 300 moles of the titanium compound are used permole of the magnesium compound used to make the solid procatalystcomposition.

The Ziegler-Natta procatalyst composition may also include an inertsupport material. The support material may be an inert solid which doesnot adversely alter the catalytic performance of the transition metalcompound. Exemplary inert support materials include metal oxides, suchas alumina, and metalloid oxides, such as silica.

Cocatalyst

The non-phthalate catalyst system may further comprise an organometalliccocatalyst. The metal element in the organometallic cocatalyst is aGroup 13 metal, for instance, aluminum. Suitable organoaluminumcompounds include those having at least one aluminum-carbon bond in themolecule, such as alkylaluminum, alkylaluminum hydride, alkylaluminumhalide, and alkylaluminum alkoxide containing from 1-10 or 1-6 carbonatoms in each alkyl or alkoxide group. Exemplary organoaluminumcompounds are trialkyl aluminums, such as triethyl aluminum and tributylaluminum; trialkenyl aluminums such as triisoprenyl aluminum; dialkylaluminum alkoxides such as diethyl aluminum ethoxide and dibutylaluminum butoxide; alkyl aluminum sesquialkoxides such as ethyl aluminumsesquiethoxide and butyl aluminum sesquibutoxide; dialkyl aluminumhalides such as diethyl aluminum chloride, dibutyl aluminum chloride anddiethyl aluminum bromide; alkyl aluminum sesquihalides such as ethylaluminum sesquichloride, butyl aluminum sesquichloride, and ethylaluminum sesquibromide; partially halogenated alkyl aluminums, e.g.,alkyl aluminum dihalides such as ethyl aluminum dichloride, propylaluminum dichloride, and butyl aluminum dibromide; dialkyl aluminumhydrides such as diethyl aluminum hydride and dibutyl aluminum hydride;other partially hydrogenated alkyl aluminum, e.g., alkyl aluminumdihydrides such as ethyl aluminum dihydride and propyl aluminumdihydride; and partially alkoxylated and halogenated alkyl aluminums,such as ethyl aluminum ethoxychloride, butyl aluminum butoxychloride,and ethyl aluminum ethoxybromide.

The organometallic cocatalyst used in the non-phthalate catalyst systemis in an amount that the molar ratio of the metal in the organometalliccocatalyst to transition metal in the Ziegler-Natta procatalystcomposition is from about 5 to about 1000, for instance, from about 10to about 700, from about 25 to about 400, or from about 100 to about300.

External Donor

The non-phthalate catalyst system also includes one or more non-silaneexternal electron donor compounds. The external electron donor is acompound added independent of the Ziegler-Natta procatalyst formation,and contains at least one functional group that is capable of donating apair of electrons to a metal atom. The external electron donor compoundserves as one component of the non-phthalate Ziegler-Natta catalystsystem for olefin polymerization, often contributing to the ability toobtain a polymer having a controllable molecular weight distribution andcontrollable crystallinity. In fact, when an external donor compound isabsent, the isotactic index of the resulting polymer is not sufficientlyhigh even if the internal donor is used. Also, for the non-phthalatecatalyst system, the conventional alkoxysilane external donors oftentimes do not have significant modifying effect on the performance of thenon-phthalate catalyst system. The non-silane external donors below arechemically different from alkoxysilanes and provide improvements in theperformance of the non-phthalate catalyst system.

The external donor compound is used in the non-phthalate catalyst systemin an amount that the molar ratio of the total external donor compoundsto the transition metal in the Ziegler-Natta procatalyst composition(e.g., titanium compound) ranges from about 0.5 to about 90, forinstance, from about 1 to about 70, or from about 1 to about 30.

i) Triester Compound

The external electron donor can be a triester compound having a formulaof

Each R is independently a C₁-C₁₀ hydrocarbyl group. For instance, each Ris a C₁ to C₁₀ alkyl, such as methyl, ethyl, or isobutyl; optionallysubstituted with methyl, isobutyl, or 2-ethylhexyl. Each R′ isindependently H or R. Each n is independently an integer from 1 to 4,for instance, from 1 to 2, or 1. The integer n′ ranges from 0 to 4, forinstance, from 0 to 2 or 0. A typical triester compound is glyceryltriacetate (

also referred to as triacetin), in which R is methyl, R′ is H, n is 1,and n′ is 0.

ii) Diester Compound

The external electron donor can be a diester compound having a formulaof

X is CH₂ or O. Each R is independently a C₁-C₁₀ hydrocarbyl group. Forinstance, each R is a C₁ to C₁₀ alkyl, such as methyl, ethyl, orisobutyl; optionally substituted with methyl, isobutyl, or 2-ethylhexyl.Each R′ is independently H or R. Each n is independently an integer from1 to 4, for instance, from 1 to 2. Typical diester compounds includethose having R as methyl, R′ as H, and n as 2. For instance, two typicaldiester compounds are 1,5-pentanediol diacetate (PDOA,

and diethyleneglycol diacetate (DEGA,

iii) Oxo-Substituted Diester Compound

The external electron donor can be an oxo-substituted triester compoundhaving a formula of

Each R is independently a C₁-C₁₀ hydrocarbyl group. For instance, each Ris a C₁ to C₁₀ alkyl, such as methyl, ethyl, or isobutyl; optionallysubstituted with methyl, isobutyl, or 2-ethylhexyl. Each R′ isindependently H or R. Each n is independently an integer from 1 to 4,for instance, from 1 to 2. A typical oxo-substituted triester compoundis diethyl-4-oxopimelate (DEOP,

in which each R is methyl, each R′ is H, and each n is 2.

A second aspect of the invention relates to a non-phthalate catalystsystem for olefin polymerization. The non-phthalate catalyst systemcomprises (a) a solid Ziegler-Natta catalyst composition comprising atransition metal, a Group 2 metal, and one or more halogens; and one ormore internal electron donor compounds; and (b) one or more externalelectron donor compounds.

The internal electron donor compound is i) a diester compound having aformula of

or ii) a cyclic diester compound having a formula of

In these formulas, each R₅ is independently a C₁ to C₁₈ hydrocarbylgroup which can optionally form one or more saturated or unsaturatedmono- or poly-cyclic structures. Each R₁₇ is independently H, halogen,or C₁ to C₁₈ hydrocarbyl group which can optionally form one or moresaturated or unsaturated cyclic structures with the phenyl group it isattached to. Each R₉ is independently H, halogen, or C₁ to C₁₈hydrocarbyl group. Each R₁₀ is independently C₁ to C₂₀ hydrocarbylgroup. Each of R₁₁ and R₁₂ is independently R₉ or —COOR₁₀, provided thatat least one of R₁₁ and R₁₂ is —COOR₁₀. Each m′ is independently aninteger from 0 to 5. The integer p ranges from 1 to 6. Each of R₅, R₉,and R₁₇ can contain one or more heteroatoms, selected from the groupconsisting of halogens, P, N, O, S, and Si, that replace one or morecarbon atoms in the hydrocarbyl group.

In certain embodiments, the internal donor is a diester compound havinga formula of

The definition of m′, R₅, and R₁₇, and the exemplary embodiments for them′, R₅, and R₁₇ groups are the same as those described for formula IIein the first aspect of the invention.

A typical diester compound has a formula of:

The definition of m′, R₁₆, and R₁₇ and the exemplary embodiments for them′, R₁₆, and R₁₇ groups are the same as those described for formula IIfin the first aspect of the invention. The exemplary 1,8-napthalenediester compounds are the same as those exemplary 1,8-napthalene diestercompounds described for formula IIf in the first aspect of theinvention.

Additional exemplary 1,8-napthalene diester compounds described forformula IIe in the first aspect of the invention also can be used inthis aspect of the invention as the internal electron donor.

In certain embodiments, the internal donor is a cyclic diester compoundhaving a formula of

The definitions of p, R₉, R₁₀, R₁₁, and R₁₂ and the exemplaryembodiments for the p, R₉, R₁₀, R₁₁, and R₁₂ groups are the same asthose described for formula III in the first aspect of the invention.

A typical cyclic diester compound has a formula of

The definitions of R₉ and R₁₀, and the exemplary embodiments for the R₉and R₁₀ groups are the same as those described for formula IIIa and IIIbin the first aspect of the invention. The exemplary cyclic diestercompounds are the same as those exemplary cyclic diester compoundsdescribed for formulas IIIa and IIIb in the first aspect of theinvention.

The non-phthalate catalyst system also includes one or more externalelectron donor compounds having a formula of

The external electron donor compound does not contain an alkoxysilanecompound. In formula VIII, each R is independently a C₁ to C₁₀hydrocarbyl group, and can contain one or more heteroatoms, selectedfrom the group consisting of halogens, P, N, O, S, and Si, that replaceone or more carbon atoms in the hydrocarbyl group. R′ is H or R. Forinstance, each R is a C₁ to C₁₀ alkyl, such as methyl, ethyl, propyl,butyl, or hexyl; C₃-C₈ cycloalkyl, such as C₅-C₆ cycloalkyl; or C₃-C₈heterocycloalkyl, such as C₅-C₆ heterocycloalkyl containing one or moreheteroatoms N, O, or S (e.g., piperidinyl); each of these groups can beoptionally substituted with one or more C₁ to C₁₀ alkyl, such as methyl,ethyl, isobutyl, or 2-ethylhexyl. The integer n ranges from 1 to 10, forinstance, from 1 to 8.

Exemplary external electron donor compounds for formula VIII includethose containing R as methyl, ethyl, propyl, butyl, hexyl, orpiperidinyl; optionally substituted with one or more C₁-C₆ alkyl; R′ asH; and n as 1 to 8. Typical external electron donor compounds forformula VIII are diethyl malonate, diethyl succinate, diethyl glutarate,diethyl adipate, diisopropyl adipate, dibutyl adipate, diisobutyladipate, bis(2-ethylhexyl) adipate, diethyl pimelate, diethyl azelate,diethyl sebacate, and bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate

In this aspect of the invention, the transition metal compound and Group2 metal compounds in the Ziegler-Natta procatalyst, and the preparationof solid Ziegler-Natta procatalyst composition are the same as thosedescribed in the first aspect of the invention. The organometalliccocatalyst in the non-phthalate catalyst system is the same as thosedescribed in the first aspect of the invention.

Process of Polymerization

Another aspect of the invention relates to a process for preparing apolyolefin. The process comprises polymerizing one or more olefins, inthe presence of the non-phthalate catalyst system under reactionconditions known by one skilled in the art sufficient to form thepolyolefin. The non-phthalate catalyst system may be any non-phthalatecatalyst system described herein according to the embodiments in thefirst and second aspects of the invention.

The reaction conditions are temperature and pressure ranges within apolymerization reactor suitable for promoting polymerization and/orcopolymerization between one or more olefins and the non-phthalatecatalyst system to form the desired polymer. The polymerization processmay be performed in any manner including gas phase, slurry, or a bulkpolymerization process, with the polymerization occurring in one or morereactor(s).

The olefins may be linear or branched olefins having 2 to 20 carbonatoms, 2 to 16 carbon atoms, or 2 to 12 carbon atoms. Typically, theolefin used to prepare the polyolefin is an α-olefin. Exemplary linearor branched α-olefins includes, but are not limited to, ethylene,propylene, 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene,4-methyl-1-pentene, 3-methyl-1-pentene, 1-hexene,3,5,5-trimethyl-1-hexene, 4,6-dimethyl-1-heptene, 1-octene, 1-decene,1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and1-eicocene. For instance, the olefin used to prepare a polyolefin ispropylene. These olefins may contain one or more heteroatoms such as anoxygen, nitrogen, or silicon. The olefin may be used individually or inmixture, either the gaseous state or the liquid state.

The polymerization process may include a pre-activation step.Pre-activation includes contacting the Ziegler-Natta procatalystcomposition with the cocatalyst and the external electron donorcompound. The resulting preactivated catalyst stream is subsequentlyintroduced into the polymerization reaction zone and contacted with theolefin monomer to be polymerized. Optionally, one or more of theexternal electron donor components may be added at this time.Pre-activation results in the combination of the procatalyst compositionwith the cocatalyst and the external electron donor compounds.

Alternatively, the polymerization process may include apre-polymerization step. Pre-polymerization includes contacting a smallamount of the olefin with the Ziegler-Natta procatalyst compositionafter the procatalyst composition has been contacted with the cocatalystand the external donor compound. Then, the resulting preactivatedcatalyst stream is introduced into the polymerization reaction zone andcontacted with the remainder of the olefin monomer to be polymerized.Optionally, one or more of the external electron donor components may beadded at this time. Pre-polymerization results in the procatalystcomposition being combined with the cocatalyst and the external electrondonor compounds, with the combination being dispersed in a matrix of thepolymer during polymerization, to facilitate the polymerization.

Typically, a catalyst is considered to be pre-polymerized when theamount of the polymer produced is from about 0.1 to about 1000 gram pergram of the solid catalyst system. The pre-polymerization step can becarried out at temperatures from about 0° C. to about 80° C., forinstance, from 5° C. to 50° C., in liquid or gas phase. Thepre-polymerization step can be performed in-line as a part of acontinuous polymerization process or separately in a batch process.

Any kind of polymerization process suitable for preparing a polyolefincan be used with the non-phthalate catalyst system. The polymerizationcan be carried out, for example, in bulk phase using a liquid monomer(e.g., propylene) as a reaction medium, in slurry using an inert liquid(e.g., hydrocarbon) as a diluent, in solution using either monomers orinert hydrocarbons as solvent for the nascent polymer, or in gas phase,operating in one or more fluidized or mechanically agitated bedreactors.

The polymerization process can be a gas phase polymerization process,operating in one or more reactors. A suitable gas phase polymerizationprocess includes the use of condensing mode as well as super condensingmode wherein gaseous components (including addition of inert low boilingcompounds) are injected into the reactor in liquid form. When multiplereactors are employed, it is desirable that they operate in series,e.g., the effluent from the first reactor is charged to the secondreactor, with an additional monomer (for homopolymerization) ordifferent monomer (for copolymerization) added to continue thepolymerization. Additional amount of the same or different non-phthalatecatalyst system or catalyst components (e.g., the procatalystcomposition, cocatalyst, or external donor compound) may be added.

As an example, the polymerization process includes preparing anethylene-propylene copolymer by contacting propylene and ethylene withthe non-phthalate catalyst system. For instance, the polymerizationprocess can be conducted in two reactors in which two olefins, such aspropylene and ethylene, are contacted to prepare a copolymer.Polypropylene is prepared in the first reactor by a bulk phase (e.g.,solution) homopolymerization, and a copolymer of ethylene and propyleneis prepared in the second reactor in the presence of the polypropylenefrom the first reactor by a gas phase copolymerization. Alternatively,the polymerization process can be conducted in one reactors but in twosequential steps, with a bulk phase homopolymerization of polypropylenein the first step, and a gas phase copolymerization of ethylene andpropylene in the presence of the polypropylene in the second step. Thisprocess is exemplified in Example 2. Regardless of the polymerizationtechnique employed, it is understood that the procatalyst composition,the cocatalyst, and the external electron donor thereof may be contactedin the absence of other polymerization components, especially monomer,prior to addition to the reactor.

The temperature of the polymerization process can range from about 20 toabout 130° C., from about 60 to about 100° C., or from about 70° C. toabout 85° C. For instance, when the polymerization is carried out in gasphase, the temperature of the polymerization process can range fromabout 75 to about 85° C., for instance at about 80° C.; when thepolymerization is carried out in bulk phase, the temperature of thepolymerization process can range from about 70 to about 80° C., forinstance at about 75° C. When the polymerization is carried out in gasphase, the operating pressure generally ranges from about 0.5 to about10 MPa, from about 0.9 to about 5 MPa, or from about 4 to about 5 MPa.In the bulk polymerization, the operating pressure generally ranges fromabout 0.5 to about 6 MPa, from about 0.9 to about 4 MPa, or from about3.5 to about 4 MPa.

The resulting polymer prepared according to the above process, using thenon-phthalate catalyst system described in this invention, has animproved isotacticity. Moreover, the resulting polymer preparedaccording to the process of the invention has an improved hydrogenresponse characterized by melt flow rate. Surprisingly, the polymerprepared by the non-phthalate catalyst system described in thisinvention, with the non-silane external donors, can have improvedhydrogen response and isotacticity at the same time. This is surprisingbehavior because, in a typical Ziegler-Natta catalyst system, theexternal donors that increase hydrogen response (i.e., characterized byMFR) typically decrease isotacticity (i.e., characterized by increased %XS).

In some embodiments, the non-phthalate catalyst system used contains theinternal electron donor compound that is a diether compound having aformula of

and the external electron donor compound that is a triester compoundhaving a formula of

or a diester compound having a formula of

The definitions of R₃, R₄, R₁₅, R, R′, q, and n are the same as thosedescribed for formula Ib, V, and VI in the first aspect of theinvention. The exemplary internal donor compounds and external donorcompounds are the same as those exemplary compounds described forformulas Ib, V, and VI in the first aspect of the invention.

For instance, in a typical non-phthalate catalyst system, the internalelectron donor compound is 9,9-bis(methoxymethyl)fluorene, and theexternal electron donor compound is triacetin, 1,5-pentanedioldiacetate, diethyl-4-oxopimelate, or diethyleneglycol diacetate. Forinstance, one non-phthalate catalyst system uses9,9-bis(methoxymethyl)fluorene as the internal electron donor compoundand triacetin as the external electron donor compound; anothernon-phthalate catalyst system uses 9,9-bis(methoxymethyl)fluorene as theinternal electron donor compound and diethyl-4-oxopimelate as theexternal electron donor compound. In these embodiments, the polymerprepared according to the process of the invention has an improvedisotacticity. Moreover, the resulting polymer prepared according to theprocess of the invention has an improved hydrogen response characterizedby melt flow rate. Surprisingly, the polymer prepared by thenon-phthalate catalyst system described in this invention, with thenon-silane external donors, can have improved hydrogen response andisotacticity at the same time. This is surprising behavior because, in atypical Ziegler-Natta catalyst system, the external donors that increasehydrogen response (i.e., characterized by MFR) mostly decreaseisotacticity (i.e., characterized by increased % XS).

In some embodiments, the non-phthalate catalyst system used contains theinternal electron donor compound that is a diester compound having aformula of

and one or more external electron donor compounds having a formula of

The definitions of R₁₆, R₁₇, R, R′, m′, and n are the same as thosedescribed for formula IIf and VIII in the first and second aspect of theinvention. The exemplary internal donor compounds and external donorcompounds are the same as those exemplary compounds described forformulas IIf and VIII in the first and second aspect of the invention.

For instance, in a typical non-phthalate catalyst system, the internalelectron donor compound is 1,8-naphthyl dibenzoate, and the externalelectron donor compound is diethyl adipate, diethyl pimelate, diethylsebacate, triacetin, Tinuvin 770® (bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate), 1,5-pentanediol diacetate, diethyl-4-oxopimelate, ordiethyleneglycol diacetate. For instance, one non-phthalate catalystsystem uses 1,8-naphthyl dibenzoate as the internal electron donorcompound and triacetin as the external electron donor compound; anothernon-phthalate catalyst system uses 1,8-naphthyl dibenzoate as theinternal electron donor compound and diethyl-4-oxopimelate as theexternal electron donor compound. In these embodiments, the polymerprepared according to the process of the invention has an improvedisotacticity. Moreover, the resulting polymer prepared according to theprocess of the invention has an improved hydrogen response characterizedby melt flow rate. Surprisingly, the polymer prepared by thenon-phthalate catalyst system described in this invention, with thenon-silane external donors, can have improved hydrogen response andisotacticity at the same time. This is surprising behavior because, in atypical Ziegler-Natta catalyst system, the external donors that increasehydrogen response (i.e., characterized by MFR) mostly decreaseisotacticity (i.e., characterized by increased % XS).

In some embodiments, the non-phthalate catalyst system used contains theinternal electron donor compound that is a cyclic diester compoundhaving a formula of

and one or more external electron donor compounds having a formula of

The definitions of R₉, R₁₀, R, R′, and n are the same as those describedfor formula IIIa, IIIb, and VIII in the first and second aspect of theinvention. The exemplary internal donor compounds and external donorcompounds are the same as those exemplary compounds described forformulas IIIa, IIIb, and VIII in the first and second aspect of theinvention.

For instance, in a typical non-phthalate catalyst system, the internalelectron donor compound is selected from the group consisting ofdiisobutyl cyclohexane-1,2-dicarboxylate, diethyl3-methylcyclohexane-1,2-dicarboxylate, di-n-propyl3-methylcyclohexane-1,2-dicarboxylate, diisopropyl3-methylcyclohexane-1,2-dicarboxylate, di-n-butyl3-methylcyclohexane-1,2-dicarboxylate, diisobutyl3-methylcyclohexane-1,2-dicarboxylate, dihexyl3-methylcyclohexane-1,2-dicarboxylate, diheptyl3-methylcyclohexane-1,2-dicarboxylate, dioctyl3-methylcyclohexane-1,2-dicarboxylate, di-2-ethylhexyl3-methylcyclohexane-1,2-dicarboxylate, didecyl3-methylcyclohexane-1,2-dicarboxylate, diethyl4-methylcyclohexane-1,3-dicarboxylate, diisobutyl4-methylcyclohexane-1,3-dicarboxylate, diethyl4-methylcyclohexane-1,2-dicarboxylate, di-n-propyl 4-methylcyclohexane-1,2-dicarboxylate, diisopropyl4-methylcyclohexane-1,2-dicarboxylate, di-n-butyl4-methylcyclohexane-1,2-dicarboxylate, diisobutyl4-methylcyclohexane-1,2-dicarboxylate, dihexyl4-methylcyclohexane-1,2-dicarboxylate, diheptyl4-methylcyclohexane-1,2-dicarboxylate, dioctyl4-methylcyclohexane-1,2-dicarboxylate, di-2-ethylhexyl4-methylcyclohexane-1,2-dicarboxylate, didecyl4-methylcyclohexane-1,2-dicarboxylate, diethyl5-methylcyclohexane-1,3-dicarboxylate, diisobutyl5-methylcyclohexane-1,3-dicarboxylate, diethyl3,4-dimethylcyclohexane-1,2-dicarboxylate, di-n-propyl3,4-dimethylcyclohexane-1,2-dicarboxylate, diisopropyl3,4-dimethylcyclohexane-1,2-dicarboxylate, di-n-butyl3,4-dimethylcyclohexane-1,2-dicarboxylate, diisobutyl3,4-dimethylcyclohexane-1,2-dicarboxylate, dihexyl3,4-dimethylcyclohexane-1,2-dicarboxylate, diheptyl3,4-dimethylcyclohexane-1,2-dicarboxylate, dioctyl3,4-dimethylcyclohexane-1,2-dicarboxylate, di-2-ethylhexyl3,4-dimethylcyclohexane-1,2-dicarboxylate, didecyl3,4-dimethylcyclohexane-1,2-dicarboxylate, diethyl3,6-dimethylcyclohexane-1,2-dicarboxylate, di-n-propyl3,6-dimethylcyclohexane-1,2-dicarboxylate, diisopropyl3,6-dimethylcyclohexane-1,2-dicarboxylate, di-n-butyl3,6-dimethylcyclohexane-1,2-dicarboxylate, diisobutyl3,6-dimethylcyclohexane-1,2-dicarboxylate, dihexyl3,6-dimethylcyclohexane-1,2-dicarboxylate, diheptyl3,6-dimethylcyclohexane-1,2-dicarboxylate, dioctyl3,6-dimethylcyclohexane-1,2-dicarboxylate, di-2-ethylhexyl3,6-dimethylcyclohexane-1,2-dicarboxylate, didecyl3,6-dimethylcyclohexane-1,2-dicarboxylate, diethyl3,6-diphenylcyclohexane-1,2-dicarboxylate, di-n-propyl3,6-diphenylcyclohexane-1,2-dicarboxylate, diisopropyl3,6-diphenylcyclohexane-1,2-dicarboxylate, di-n-butyl3,6-diphenylcyclohexane-1,2-dicarboxylate, diisobutyl3,6-diphenylcyclohexane-1,2-dicarboxylate, dihexyl3,6-diphenylcyclohexane-1,2-dicarboxylate, dioctyl3,6-diphenylcyclohexane-1,2-dicarboxylate, didecyl3,6-diphenylcyclohexane-1,2-dicarboxylate, diethyl3-methyl-6-ethylcyclohexane-1,2-dicarboxylate, di-n-propyl3-methyl-6-ethylcyclohexane-1,2-dicarboxylate, diisopropyl3-methyl-6-ethylcyclohexane-1,2-dicarboxylate, di-n-butyl3-methyl-6-ethylcyclohexane-1,2-dicarboxylate, diisobutyl3-methyl-6-ethylcyclohexane-1,2-dicarboxylate, dihexyl3-methyl-6-ethylcyclohexane-1,2-dicarboxylate, diheptyl3-methyl-6-ethylcyclohexane-1,2-dicarboxylate, dioctyl3-methyl-6-ethylcyclohexane-1,2-dicarboxylate, di-2-ethylhexyl3-methyl-6-ethylcyclohexane-1,2-dicarboxylate, didecyl3-methyl-6-ethylcyclohexane-1,2-dicarboxylate, diethyl3-methyl-6-ethylcyclohexane-1,2-dicarboxylate, di-n-propyl3-methyl-6-ethylcyclohexane-1,2-dicarboxylate, diisopropyl3-methyl-6-ethylcyclohexane-1,2-dicarboxylate, di-n-butyl3-methyl-6-ethylcyclohexane-1,2-dicarboxylate, diisobutyl3-methyl-6-ethylcyclohexane-1,2-dicarboxylate, dihexyl3-methyl-6-ethylcyclohexane-1,2-dicarboxylate, diheptyl3-methyl-6-ethylcyclohexane-1,2-dicarboxylate, dioctyl3-methyl-6-ethylcyclohexane-1,2-dicarboxylate, di-2-ethylhexyl3-methyl-6-ethylcyclohexane-1,2-dicarboxylate, didecyl3-methyl-6-ethylcyclohexane-1,2-dicarboxylate, diethyl3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate, di-n-propyl3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate, diisopropyl3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate, di-n-butyl3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate, diisobutyl3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate, dihexyl3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate, diheptyl3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate, dioctyl3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate, di-2-ethylhexyl3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate, dodecyl3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate, diethyl3-hexylcyclohexane-1,2-dicarboxylate, diisobutyl3-hexylcyclohexane-1,2-dicarboxylate, diethyl3,6-dihexylcyclohexane-1,2-dicarboxylate, and diisobutyl3-hexyl-6-pentylcyclohexane-1,2-dicarboxylate; and the external electrondonor compound is diethyl adipate, diethyl pimelate, diethyl sebacate,triacetin, 1,5-pentanediol diacetate, diethyl-4-oxopimelate, ordiethyleneglycol diacetate. For instance, the non-phthalate catalystsystem uses one of the above-listed compounds as the internal electrondonor compound, and triacetin or diethyl-4-oxopimelate as the externalelectron donor compound. In these embodiments, the polymer preparedaccording to the process of the invention has an improved isotacticity.an improved hydrogen response characterized by melt flow rate, and insome cases an increased gas phase activity and/or broadened molecularweight distribution. Surprisingly, the polymer prepared by thenon-phthalate catalyst system described in this invention, with thenon-silane external donors, can have improved hydrogen response andisotacticity at the same time. This is surprising behavior because, in atypical Ziegler-Natta catalyst system, the external donors that increasehydrogen response (i.e., characterized by MFR) mostly decreaseisotacticity (i.e., characterized by increased % XS).

Additional aspects, advantages and features of the invention are setforth in this specification, and in part will become apparent to thoseskilled in the art on examination of the following, or may be learned bypractice of the invention. The inventions disclosed in this applicationare not limited to any particular set of or combination of aspects,advantages and features. It is contemplated that various combinations ofthe stated aspects, advantages and features make up the inventionsdisclosed in this application.

EXAMPLES

The following examples are for illustrative purposes only and are notintended to limit, in any way, the scope of the present invention.

Materials & Procedures

Table 1 lists the phthalate catalysts tested as reference systems (orcomparative examples).

TABLE 1 Phthalate catalysts tested as reference systems: ComparativeCatalyst Example Internal Donor 1 Diisobutylphthalate 2Diisobutylphthalate 3 Diisobutylphthalate 4 Di-n-butylphthalate

The alkoxysilanes used as reference systems in the comparative exampleswere C-donor (cyclohexylmethyl dimethoxysilane), D-donor (dicyclopentyldimethoxysilane), P-donor (diisopropyl dimethoxysilane), and DIBS(diisobutyl dimethoxysilane).

Table 2 lists the non-phthalate procatalysts falling within the scope ofthis invention, listed below as Catalyst Example Nos. 1-5.

TABLE 2 Non-phthalate catalysts tested Catalyst Example No. InternalDonor 1 9,9-bis(methoxymethyl)fluorene [“Diether”] 2 1,8-Napthyldibenzoate 3 Cyclohexanedicarboxylate ester 4 Cyclohexanedicarboxylateester 5 Cyclohexanedicarboxylate ester

Structures of the non-silane aliphatic ester external donors, tested incombination with Catalyst Example Nos. 1-5, are shown below.

Diesters:

Diethyl malonate (n = 1, R = ethyl) Diethyl glutarate (n = 3, R = ethyl)Diethyl adipate (n = 4, R = ethyl) Diisopropyl adipate (n = 4, R =isopropyl) Dibutyl adipate (n = 4, R = n-butyl or isobutyl) Bis(2-ethylhexyl) adipate (n = 4, R = 2-ethylhexyl) Diethyl pimelate (n =5, R = ethyl) Diethyl azelate (n = 7, R = ethyl) Diethyl sebacate (n =8, R = ethyl) Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (Tinuvin ®770) (n = 8, R = 2,2,6,6-tetramethyl-4- piperidyl) Triester:

Glyceryl Triacetate (Triacetin) Diacetates:

1,5-Pentanediol Diacetate (PDOA)

Diethyleneglycol diacetate (DEGA)

Diethyl-4-oxopimelate (DEOP)

Polymerizations were carried out in either a 1- or 2-gallon autoclavereactor in bulk liquid propylene (2000 grams in 1 gallon, 3000 grams in2 gallon). Polymerization temperature and the amount of hydrogen addedvaried. Prior to the polymerization, triethylaluminum (TEAL), externaldonor, and procatalysts (including the internal donors) were injected tothe reactor sequentially at room temperature and low pressure (<5 psig).Propylene and hydrogen were then added, and the reactor temperature wasincreased to the desired set point.

Impact copolymers were made by sequential bulk homopolymerization andgas phase copolymerization in a 2 gallon reactor. After thehomopolymerization stage (at 75° C.), the reactor was depressured andpurged with N₂ for 15 minutes before feeding ethylene, propylene, andhydrogen gas into the reactor. The gases were fed continuously to thereactor and constant pressure was maintained using a back pressureregulator thus ensuring a constant gas ratio. The gas phasecopolymerization conditions were: 80° C., 140 psi, and molar ratios ofthe components in the gas phase are: ethylene/(ethylene+propylene)=0.43;and H₂/ethylene=0.067.

Molecular weight distribution of the polymers was measured by either GPC(M_(w)/M_(n)) or dynamic rheology (Polydispersity Index—PI). Polymerisotacticity was measured by xylene fractionation (% XS) or 500 MHz ¹³CNMR (Bruker). DSC thermal fractionation was carried out by heating asample to 200° C. at 10° C./minute, equilibrating for two hours, andthen lowering the temperature by 10° C. increments to 120° C. The samplewas allowed to equilibrate for two hours at each successive temperature.At the end of this cycle, the sample was heated up to 200° C. at 10°C./minute, and the melting endotherm was measured.

Results and Discussion

The different phthalate and non-phthalate procatalyst systems listed inTable 1 and Table 2, respectively, were analyzed with conventionalalkoxysilane external donors and analyzed in Table 3 and Table 4,respectively, below.

Unlike phthalate-based catalysts, most non-phthalate catalysts are notstrongly influenced by the type of alkoxysilane external donor used.This is illustrated in Table 4 for several different non-phthalatesystems. Note that the ranges of MFR and % XS are much narrower for thephthalate procatalysts in Table 3 than for the non-phthalateprocatalysts in Table 4.

TABLE 3 The phthalate procatalysts with conventional alkoxysilaneexternal donors Comparative kg Catalyst External Polypropylene/ %Example No. Donor g Procatalyst MFR XS 1¹ C-donor 35 80 4.0 P-donor 3370 3.0 D-donor 30 25 2.7 1² C-donor 31 120 3.3 P-donor 34 100 2.9D-donor 38 40 2.8 2² C-donor 34 100 3.0 P-donor 40 80 2.5 D-donor 44 252.0 3³ C-donor 38 8 2.6 P-donor 36 3 2.2 D-donor 35 2 2.2 DIBS 34 6 3.53⁴ C-donor 38 20 2.7 P-donor 39 10 2.1 DIBS 39 20 2.7 ¹2-gallon reactor,70° C., 3.5 g H₂, ratio of donor/Ti compound = 10 ²2-gallon reactor, 75°C., 4.75 g H₂, ratio of donor/Ti compound = 10 ³1-gallon reactor, 75°C., 0.6 g H₂, ratio of donor/Ti compound = 10 ⁴1-gallon reactor, 75° C.,0.9 g H₂, ratio of donor/Ti compound = 10

TABLE 4 The non-phthalate procatalysts (see Table 2 for internal donorsfor each example) with conventional alkoxysilane external donors(1-gallon reactor, 75° C., ratio of donor/Ti compound = 10) kg CatalystExternal Polypropylene/ % Example Donor g Procatalyst MFR XS 1 C-Donor40 45 1.4 P-Donor 40 50 1.5 D-Donor 39 50 1.4 2 C-Donor 47 4 2.0 P-Donor44 9 2.0 D-Donor 43 8 1.7 3 C-Donor 33 20 2.4 P-Donor 33 30 2.5 D-Donor30 15 2.4 4 C-Donor 29 6 2.4 P-Donor 30 8 2.2 5 C-Donor 35 28 2.9D-Donor 37 24 2.7

The effects of non-silane aliphatic diester external donors on differentphthalate and non-phthalate procatalyst systems listed in Table 2 wereanalyzed. As shown in results below, each of these non-phthalateprocatalysts had a particular deficiency that could not be influenced byalkoxysilanes, but were influenced by the new external donors.

Example No. 2 Procatalyst

Example No. 2 procatalyst is a non-phthalate catalyst containing1,8-napthyl dibenzoate as an internal donor (see U.S. Pat. No.8,003,558, which is incorporated herein by reference in its entirety).With typical alkoxysilane external donors (C, D, and P), Example No. 2procatalyst had a significantly lower hydrogen response compared to aphthalate catalyst (Comparative Example 4) (see FIG. 1). Furthermore,FIG. 1 also shows that the type of alkoxysilane external donor has verylittle influence on the hydrogen response of Example No. 2 procatalyst.

A series of non-silane aliphatic diester molecules were tested asexternal donors to improve the hydrogen response of Example No. 2procatalyst. The results are shown in FIG. 1, Table 5.2, and Table 5.3.Table 5.1 illustrates the Example No. 2 procatalyst with varied Do/Tiratios (1-gallon reactor, at 75° C., 1.8 gm H₂). While the aliphaticdiesters somewhat decreased the catalyst activity, the hydrogen responsegap between Example No. 2 procatalyst (non-phthalate) and ComparativeExample 4 procatalyst (phthalate) was significantly reduced, especiallyat higher hydrogen levels. In addition, the polymers produced using thenon-silane aliphatic diester external donors had a higher isotacticity(i.e., lower % XS) than those produced with the conventionalalkoxysilane external donors at the same donor level.

At least some of the activity appeared to be recovered at a lower ratioof donor/Ti compound. Therefore, lowering the ratio of donor/Ti compoundmay be desirable to provide an improved performance comparable toconventional alkoxysilane external donors. Lowering the ratio ofdonor/Ti compound may also result in lower donor residues in the finalproduct as well as providing an economic advantage over conventionalalkoxysilane external donors.

TABLE 5.1 Example No. 2 procatalyst with varied Do/Ti ratios (1-gallonreactor, at 75° C., 1.8 gm H₂) kg Polypropylene/ Donor Do/Ti gProcatalyst P-donor 10 43 30 46 Diethyl Adipate 2 49 5 47 10 33 30 11

TABLE 5.2 Comparison of Example No. 2 procatalyst with conventionalalkoxysilane external donors and with non-silane aliphatic diesterexternal donors (2-gallon reactor, at 75° C., Do/Ti = 10, 4.0 gm H₂) kgPolypropylene/ % External Donor g Procatalyst MFR XS C-donor 60 27 1.8Diethylene Gylcol Diacetate 18 71 1.6 1,5-Pentanediol Diacetate 27 541.4 Triacetin 43 45 2.6 Diethyl Malonate 73 44 3.6 Diethyl 4-0xopimelate40 41 1.8 Diethyl Adipate 35 34 1.6 Tinuvin 770 56 25 2.0

TABLE 5.3 Comparison of Example No. 2 procatalyst with conventionalalkoxysilane external donors and with non-silane aliphatic diesterexternal donors (1-gallon reactor, at 75° C., Do/Ti = 10, 1.8 gm H₂) kgPolypropylene/ % External Donor g Procatalyst MFR XS C-Donor 46 37 2.2D-Donor 48 24 2.2 P-Donor 43 43 2.1 Diethyl Sebacate 31 94 1.5 DiethylPimelate 34 83 2.2 Diethyl Adipate 33 81 1.5 Diisopropyl Adipate 46 472.2 Dibutyl Adipate 42 44 2.1 Diethyl Azelate 41 42 2.0 DiethylGlutarate 46 41 2.7 Diethyl Malonate 51 25 3.4 Diisobutyl Adipate 50 232.6 Bis (2-ethylhexyl) Adipate 56 18 2.9

Example No. 5 Procatalyst

Example No. 5 is a non-phthalate procatalyst based on acyclohexanedicarboxylate internal donor (see U.S. Pat. Nos. 7,649,062and 7,888,438, which are incorporated herein by reference in theirentirety). Table 6 shows that Example No. 5 procatalyst withconventional alkoxysilane external donor provided somewhat lower MFR andhigher xylene solubles than Comparative Example 1 procatalyst(phthalate). However, using diethyladipate as the external donorincreased both the hydrogen response and isotacticity of Example No. 5procatalyst. The increase in isotacticity was enough to make thisnon-phthalate catalyst system comparable to Comparative Example 1 (aphthalate catalyst system).

Similar to Example No. 2 procatalyst and aliphatic diester externaldonors, the catalyst activity when using Example No. 5 procatalyst withan aliphatic diester external donor was somewhat decreased compared tothe conventional alkoxysilane external donor at the same donor/Ticompound ratio.

TABLE 6 Comparison of Example No. 5 procatalyst with conventionalalkoxysilane external donors and with non-silane aliphatic diesterexternal donors to Comparative Example 1 procatalyst (phthalate) withconventional alkoxysilane external donors (1-gallon reactor, 75° C.,ratio of donor/Ti compound = 10) kg Polypropylene/ % Catalyst ExternalDonor g H₂ g Procatalyst MFR XS Example No. 5 P-Donor 1.8 54 60 3.3 1.252 19 3.6 0.6 45 3 4.0 Example No. 5 Diethyl Adipate 1.8 38 290 2.5 1.236 78 2.5 0.6 32 8 3.2 Comparative P-donor 1.8 44 110 3.2 Example 1 1.240 30 2.6 0.6 30 3 2.7

Example No. 3 Procatalyst

Example No. 3 is a non-phthalate procatalyst based on acyclohexanedicarboxylate internal donor which produces very broad MWDproducts (see U.S. Pat. No. 8,729,189, which is incorporated herein byreference in its entirety).

A comparison of polymerization with Example No. 3 procatalyst incombination with a conventional alkoxysilane external donor and incombination with the non-silane aliphatic diester external donors isshown in Tables 7.1 and 7.2. Although the catalyst activity wasdecreased, the hydrogen response was in some cases increased by thediester external donors compared to the conventional alkoxysilaneexternal donor, isotacticity was improved and the MWD remained the sameor was broadened.

TABLE 7.1 Comparison of Example No. 3 procatalyst with a conventionalalkoxysilane external donor and non-silane aliphatic diester externaldonors (1-gallon reactor, 75° C., ratio of donor/Ti compound = 10, 1.8 gH₂) kg Polypropylene/ % External Donor g Procatalyst MFR XS C-Donor 3271 2.4 D-Donor 34 58 2.1 P-Donor 33 140 2.6 Triacetin 18 148 2.6 Diethyl4-Oxopimelate 15 146 2.2 1,5-Pentanediol Diacetate 13 125 1.7 DiethylMalonate 39 105 4.7 Diethyl Adipate 14 100 2.0 Diethyl Sebacate 16 962.0 Diethyl Pimelate 18 90 2.0 Diethylene Gylcol Diacetate 6 90 1.4Tinuvin 770 23 138 2.3

TABLE 7.2 Comparison of Example No. 3 procatalyst with a conventionalalkoxysilane external donor and non-silane aliphatic diester externaldonors (1-gallon reactor, 75° C., ratio of donor/Ti compound = 10, 0.6 gH₂) External Donor PI P-Donor 5.6 Triacetin 8.4 Diethyl 4-Oxopimelate7.8 1,5-Pentanediol Diacetate 7.8 Diethyl Adipate 7.6 Diethyl Pimelate6.5 Diethylene Gylcol Diacetate 8.8 Tinuvin 770 7.5

It was previously observed that Example No. 3 procatalyst has relativelylow gas phase activity in the production of impact copolymer compared tothe phthalate catalyst of Comparative Example 1. FIG. 2 illustrates thegap in gas phase production between Example No. 3 procatalyst(non-phthalate) and Comparative Example 1 procatalyst (phthalate) whenusing P-donor as the external donor. This shows that Example No. 3,procatalyst (non-phthalate) in combination with the conventionalalkoxysilane external donors, does not have as good of a performance asthe phthalate catalyst of Comparative Example 1 in the production of animpact copolymer.

However, when the non-silane aliphatic ester compounds were used withExample No. 3 procatalyst, much more promising gas phase production wasobserved (FIGS. 2 and 3). Diethyladipate external donor gave similar orslightly better ethylene incorporation than the phthalate/alkoxysilanesystem, and the triester donor (triacetin) improved the ethyleneincorporation beyond that of the phthalate catalyst.

Example No. 1 Procatalyst

Example No. 1 is a commercial non-phthalate diether procatalyst (seeU.S. Pat. No. 5,723,400, which is incorporated herein by reference inits entirety). Diether catalysts typically produce polypropylenes havinglower crystallinity and stiffness than the phthalate catalysts, due to anarrower MWD and more regioirregular chain structure (Tables 8 and 10).Diether procatalysts also do not respond very differently to differentalkoxysilane donors (see Tables 4 and 8).

Example No. 1 procatalyst was tested with alternative external donors toimprove the attributes of the polymer product compared to theconventional alkoxysilane systems and to create products more similar tophthalate-based catalysts.

TABLE 8 Comparison of Example No. 1 procatalyst with conventionalalkoxysilane external donors and non-silane aliphatic ester donors(1-gallon reactor, 75° C., ratio of donor/Ti Compound = 10, 1.2 gm H₂)kg Polypropylene/ % External Donor g Procatalyst MFR XS D-donor 35 2701.5 C-donor 36 290 1.7 P-donor 37 310 2.1 Diethylene Gylcol Diacetate 19610 1.1 Diethyl 4-Oxopimelate 24 530 0.9 1,5-Pentanediol Diacetate 25490 0.9 Triacetin 31 470 1.5

One particular advantage of the alternative external donors with ExampleNo. 1 procatalyst is the increase in the isotacticity of polymers, whilethe polydispersity index (PI) appeared to be essentially unchanged(Table 9). Thus, these new donors can modify the polymer structure in away that differs from conventional alkoxysilane donors.

TABLE 9 Comparison of Example No. 1 procatalyst with conventionalalkoxysilane external donors and non-silane aliphatic ester externaldonors (1-gallon reactor, 75° C., ratio of donor/Ti Compound = 10, 0.6gm H₂) kg Polypropylene/ % External Donor g Procatalyst MFR XS PID-donor 36 3.2 1.3 3.4 C-Donor 37 3.5 1.7 — P-Donor 47 2.3 1.8 —Triacetin 27 25 1.1 3.3 Diethylene Gylcol Diacetate 14 13 1.1 3.7Diethyl 4-Oxopimelate 21 9 1.4 3.4 1,5-Pentanediol Diacetate 18 7 1.03.7

The positive effect of the alternative donors on the hydrogen responseof Example No. 1 procatalyst is illustrated in FIG. 4. As shown in FIG.4, the new external donors in combination with the diether procatalystsproduced a higher MFR product, which can lead to the production of awider range of products than currently possible with conventionalalkoxysilane external donors.

The above results show that aliphatic di- and tri-ester donors appearedto improve both hydrogen response and isotacticity at the same time.This is a desirable and novel behavior compared to the conventionalresponse of the Ziegler-Natta procatalysts to the external donors.Typically, external donors that increase MFR also decrease isotacticity(increase % XS).

Compared to conventional alkoxysilane external donors, a relativelylower activity is seen at the same donor/Ti compound with the diesterexternal donors. However, at least some of the activity appeared to berecovered at a lower donor/Ti compound. Therefore, lowering the ratio ofdonor/Ti compound may be desirable to provide an improved performancecomparable to conventional alkoxysilane external donors. Lowering theratio of donor/Ti compound may also result in lower donor residues inthe final product as well as providing an economic advantage overconventional alkoxysilane external donors.

The results of the new aliphatic ester external donors in combinationwith the non-phthalate procatalyst are surprising as the phthalatecatalysts typically do not respond well to these non-silane aliphaticester external donors. As shown in Table 10, when these non-silanealiphatic ester external donors in combination with the phthalateprocatalyst, the catalyst activity was dramatically reduced and both theMFR and % XS were significantly increased.

TABLE 10 Comparison of the phthalate procatalyst of Comparative Example1 with a conventional alkoxysilane external donor and a non-silanealiphatic diester external donor (1-gallon reactor, 75° C., ratio ofdonor/Ti Compound = 10) kg Polypropylene/ % External Donor g H₂ gProcatalyst MFR XS P-Donor 1.8 44 110 3.2 1.2 40 30 2.6 0.6 30 3 2.7Diethyl Adipate 1.8 6 1000 4.5 1.2 5 400 5.1 0.6 4 70 6.8

Although preferred embodiments have been depicted and described indetail herein, it will be apparent to those skilled in the relevant artthat various modifications, additions, substitutions, and the like canbe made without departing from the spirit of the invention and these aretherefore considered to be within the scope of the invention as definedin the claims which follow.

What is claimed is:
 1. A non-phthalate catalyst system for olefinpolymerization, comprising: (a) a solid Ziegler-Natta catalystcomposition comprising a transition metal, a Group 2 metal, and one ormore halogens; and one or more internal electron donor compounds havingthe structure of a diester compound having a formula of

wherein: each R₅ is independently a C₁ to C₁₈ hydrocarbyl group whichcan optionally form one or more saturated or unsaturated mono- orpoly-cyclic structures; each R₁₇ is independently halogen, or a C₁ toC₁₈ hydrocarbyl group which can optionally form one or more saturated orunsaturated cyclic structures with the phenyl group it attaches to; eachm′ is independently an integer from 0 to 3; and wherein each of R₅ andR₁₇ can contain one or more heteroatoms that replace one or more carbonatoms in the hydrocarbyl group, wherein the one or more heteroatoms areselected from the group consisting of halogens, P, N, O, S, and Si; and(b) one or more external electron donor compounds having a formula of

wherein: each R is independently a C₁ to C₁₀ hydrocarbyl group, and cancontain one or more heteroatoms that replace one or more carbon atoms inthe hydrocarbyl group, wherein the one or more heteroatoms are selectedfrom the group consisting of halogens, P, N, O, S, and Si; R′ is H or R,and n is an integer from 1 to 10, wherein the non-phthalate catalystsystem does not contain an alkoxysilane compound.
 2. The non-phthalatecatalyst system of claim 1, wherein the transition metal is titanium,the Group 2 metal is magnesium, and the halogen is chloride.
 3. Thenon-phthalate catalyst system of claim 1, wherein the catalyst systemfurther comprises an organoaluminum cocatalyst selected from the groupconsisting of alkylaluminum, alkylaluminum hydride, alkylaluminumhalide, and alkylaluminum alkoxide.
 4. The non-phthalate catalyst systemof claim 1, wherein the internal electron donor compound is a diestercompound having the formula (IIe), wherein m′ is 0-3, and each R₅ is aC₁-C₁₀ alkyl, C₂-C₁₀ alkenyl, C₅-C₆ cycloalkyl, C₅-C₆ cycloalkenyl,aryl, or heteroaryl; each of these groups can be further substituted byhalogen, C₁-C₁₀ alkyl, or C₁-C₁₀ alkoxy.
 5. The non-phthalate catalystsystem of claim 1, wherein the internal electron donor compound is adiester compound having a formula of:

wherein each of R₁₆ and R₁₇ is independently halogen, a C₁-C₆ alkyl,C₁-C₆ alkoxy, phenyl, C₇-C₁₂ aralkyl, or C₇-C₁₂ alkylaryl, wherein eachm′ for R₁₆ is 0 to 5, and each m′ for R₁₇ is 0 to
 3. 6. Thenon-phthalate catalyst system of claim 5, wherein the diester compoundis selected from the group consisting of 1,8-naphthyl dibenzoate;1,8-naphthyl di-4-methylbenzoate; 1,8-naphthyl di-3-methylbenzoate;1,8-naphthyl di-2-methylbenzoate; 1,8-naphthyl di-4-ethylbenzoate;1,8-naphthyl di-4-n-propylbenzoate; 1,8-naphthyl di-4-isopropylbenzoate;1,8-naphthyl di-4-n-butylbenzoate; 1,8-naphthyl di-4-isobutylbenzoate;1,8-naphthyl di-4-t-butylbenzoate; 1,8-naphthyl di-4-phenylbenzoate;1,8-naphthyl di-4-fluorobenzoate; 1,8-naphthyl di-3-fluorobenzoate;1,8-naphthyl di-2-fluorobenzoate; 1,8-naphthyl di-4-chlorobenzoate;1,8-naphthyl di-3-chlorobenzoate; 1,8-naphthyl di-2-chlorobenzoate;1,8-naphthyl di-4-bromobenzoate; 1,8-naphthyl di-3-bromobenzoate;1,8-naphthyl di-2-bromobenzoate; 1,8-naphthyl di-4-cyclohexylbenzoate;1,8-naphthyl di-2,3-dimethylbenzoate; 1,8-naphthyldi-2,4-dimethylbenzoate; 1,8-naphthyl di-2,5-dimethylbenzoate;1,8-naphthyl di-2,6-dimethylbenzoate; 1,8-naphthyldi-3,4-dimethylbenzoate; 1,8-naphthyl di-3,5-dimethylbenzoate;1,8-naphthyl di-2,3-dichlorobenzoate; 1,8-naphthyldi-2,4-dichlorobenzoate; 1,8-naphthyl di-2,5-dichlorobenzoate;1,8-naphthyl di-2,6-dichlorobenzoate; 1,8-naphthyldi-3,4-dichlorobenzoate; 1,8-naphthyl di-3,5-dichlorobenzoate; and1,8-naphthyl di-3,5-di-t-butylbenzoate.
 7. The non-phthalate catalystsystem of claim 6, wherein the diester compound is 1,8-naphthyldibenzoate.
 8. The non-phthalate catalyst system of claim 1, wherein thediester compound is selected from the group consisting of


9. The non-phthalate catalyst system of claim 1, wherein, for theexternal electron donor, each R is a C₁-C₁₀ alkyl, C₃-C₈ cycloalkyl, orC₃-C₈ heterocycloalkyl, optionally substituted with one or more alkyl,each R′ is H or CH₃, and n is an integer from 1 to
 8. 10. Thenon-phthalate catalyst system of claim 9, wherein each R is methyl,ethyl, propyl, butyl, or 2-ethyl hexyl, and each R′ is H.
 11. Thenon-phthalate catalyst system of claim 9, wherein each R is piperidinyl,optionally substituted with one or more C₁-C₆ alkyl; and each R′ is H.12. The non-phthalate catalyst system of claim 1, wherein the one ormore heteroatoms that can replace one or more carbon atoms in thehydrocarbyl group are selected from the group consisting of halogens, P,N, O, and S.